Methods and devices for forming nanostructure monolayers and devices including such monolayers

ABSTRACT

Methods for forming or patterning nanostructure arrays are provided. The methods involve formation of arrays on coatings comprising nanostructure association groups, formation of arrays in spin-on-dielectrics, solvent annealing after nanostructure deposition, patterning using resist, and/or use of devices that facilitate array formation. Related devices for forming nanostructure arrays are also provided, as are devices including nanostructure arrays (e.g., memory devices). Methods for protecting nanostructures from fusion during high temperature processing also are provided.

CROSS-REFERENCE TO RELATED APPLICATIONS

This application is a division of U.S. patent application Ser. No.13/098,082 filed Apr. 29, 2011, now U.S. Pat. No. 8,558,304, which is adivision of U.S. patent application Ser. No. 11/881,739, filed Jul. 27,2007, now U.S. Pat. No. 7,968,273, which is a continuation-in-part ofU.S. patent application Ser. No. 11/495,188, filed Jul. 28, 2006, nowU.S. Pat. No. 7,776,758, which is a continuation-in-part of U.S. patentapplication Ser. No. 11/148,001, filed Jun. 7, 2005, now U.S. Pat. No.7,501,315, which claims priority to and benefit of the following priorprovisional patent applications: U.S. Provisional Patent ApplicationSer. No. 60/671,134, filed Apr. 13, 2005, U.S. Provisional PatentApplication Ser. No. 60/632,570, filed Nov. 30, 2004, and U.S.Provisional Patent Application Ser. No. 60/578,236, filed Jun. 8, 2004,each of which is incorporated herein by reference in its entirety forall purposes.

BACKGROUND

This invention relates primarily to the field of nanotechnology. Morespecifically, the invention pertains to methods and devices for formingnanostructure arrays, e.g., monolayer arrays, e.g., of predeterminedsize and/or at predetermined positions, and to devices (e.g., memorydevices) including such nanostructure arrays. The invention also relatesto methods for protecting nanostructures from fusion during hightemperature processing.

Monolayers of nanostructures (e.g., quantum dots) can serve ascomponents of a variety of optoelectronic devices such as LEDs andmemory devices (see, e.g., Flagan et al. U.S. Pat. No. 6,586,785).Methods for producing such monolayers include growing quantum dots insitu on a solid by molecular beam epitaxy, and exploiting phasesegregation between aliphatic surfactants on quantum dots and aromaticconjugated organic materials deposited on the dots (Coe et al.“Electroluminescence from single monolayers of nanocrystals in molecularorganic devices” Nature 450:800-803 (2002)). However, the formertechnique is difficult to scale up to form large numbers of monolayers,and the latter technique produces a layer of nanostructures embedded inor disposed on a thick organic matrix whose presence is undesirable inmany device fabrication processes.

Methods for simply and reproducibly forming nanostructure monolayers arethus desirable. Among other aspects, the present invention provides suchmethods. A complete understanding of the invention will be obtained uponreview of the following.

SUMMARY

Methods for patterning nanostructure arrays, e.g., ordered or disorderedmonolayer arrays, and for protecting nanostructures from fusion duringhigh temperature processing are described. Devices includingnanostructure arrays are also provided.

One general class of embodiments provides methods for patterning ananostructure monolayer. The methods include a) disposing resist and amonolayer of nanostructures on a first layer, wherein the nanostructuresare embedded in the resist, to provide a resist layer, b) exposing apredetermined pattern on the resist layer (e.g., to ionizing radiationsuch as ultraviolet light or an electron beam), to provide exposedresist in at least a first region of the resist layer and unexposedresist in at least a second region of the resist layer, c) removing theunexposed resist and its embedded nanostructures from the first layerwithout removing the exposed resist and its embedded nanostructures,whereby at least one nanostructure monolayer array defined by the firstregion remains on the first layer, and d) after step c), exposing thefirst layer, the exposed resist and its embedded nanostructures to atemperature of at least about 300° C. (e.g., at least about 700° C. orat least about 900° C.).

In one particularly useful aspect, the resist is incompletely cured byinitial low dose or brief exposure to pattern the monolayer, unexposedresist and undesired nanostructures embedded therein are removed, andthe incompletely cured resist is then further cured with a secondexposure to protect the nanostructures from subsequent high temperaturestep(s). Thus, in one class of embodiments, in step b) the resist in thefirst region is exposed to ionizing radiation sufficient to incompletelycure the resist in the first region, and then, after step c) and beforestep d), the incompletely cured resist in the first region is exposed toionizing radiation sufficient to further cure the resist in the firstregion. As one example, in step b) the resist in the first region can beexposed to about 10 mJ/cm²-1 J/cm² ultraviolet light to incompletelycure the resist in the first region, and, after step c) and before stepd), the resist in the first region can be exposed to about 1 J/cm²-50J/cm² ultraviolet light to further cure the resist in the first region.

The methods can protect the nanostructures from fusion at elevatedtemperatures, thus maintaining nanostructure density, size, sizedistribution, monolayer morphology, etc., during high temperatureprocessing steps. Accordingly, in one class of embodiments, the densityof nanostructures in the monolayer array after step d) is at least 75%of the density of nanostructures in the monolayer array before step d),more typically, at least 90% or at least 95%. Optionally, the density isessentially unchanged during step d). Optionally, following step d), themonolayer array of nanostructures has a density greater than about1×10¹⁰ nanostructures/cm², e.g., greater than about 1×10¹¹nanostructures/cm², greater than about 1×10¹² nanostructures/cm², atleast 2.5×10¹² nanostructures/cm², at least 5×10¹² nanostructures/cm²,or even at least about 1×10¹³ nanostructures/cm². Optionally, density ofthe nanostructures in the monolayer array is substantially uniformfollowing step d).

In a related class of embodiments, the average diameter of thenanostructures in the monolayer array after step d) is less than 110% ofthe average diameter of the nanostructures in the monolayer array beforestep d), for example, less than 105% or less than 103%. Optionally, thesize distribution of the nanostructures in the array is essentiallyunchanged during step d).

In another related class of embodiments, following step d), the sizedistribution of the nanostructures in the monolayer array exhibits anrms deviation of less than 20%. For example, the size distribution ofthe nanostructures in the monolayer array can exhibit an rms deviationof less than 15%, less than 10%, or even less than 5%.

It will be evident that the tendency of nanostructures to fuse isgreater at higher initial nanostructure densities, and thus protectionfrom fusion is increasingly important with increasing nanostructuredensity. Thus, in embodiments in which, e.g., preservation ofnanostructure density, monolayer uniformity, nanostructure size, and/ornanostructure size distribution is of interest, the density ofnanostructures in the monolayer array before step d) is optionally atleast about 1×10¹⁰ nanostructures/cm², e.g., at least about 1×10¹¹nanostructures/cm², at least about 1×10¹² nanostructures/cm², at least2.5×10¹² nanostructures/cm², at least 5×10¹² nanostructures/cm², or evenat least about 1×10¹³ nanostructures/cm².

The resist layer can be formed in step a) by essentially any convenienttechnique. For example, the first layer can be spin coated with asolution comprising the resist and the nanostructures. Similarly,unexposed resist can be removed in step c) by essentially any convenienttechnique. For example, the unexposed resist and its embeddednanostructures can be removed from the first layer without removing theexposed resist and its embedded nanostructures by contacting theunexposed resist with at least one organic solvent.

In one class of embodiments, the resist comprises a silicon compound.For example, the resist can be a silsesquioxane, such asmercapto-propyl-cyclohexyl polyhedral oligomeric silsesquioxane,hydrogen silsesquioxane, methyl silsesquioxane, octavinyl dimethyl silylsilsesquioxane, octasilane silsesquioxane, octavinyl-T8 silsesquioxane,aminopropylcyclohexyl polyhedral oligomeric silsesquioxane, acrylosilsesquioxane, or methacrylo silsesquioxane.

The methods can be used to produce essentially any number of monolayerarrays. For example, exposed resist can be provided in two or more, 10or more, 50 or more, 100 or more, 1000 or more, 1×10⁴ or more, 1×10⁶ ormore, 1×10⁹ or more, 1×10¹⁰ or more, 1×10¹¹ or more, or 1×10¹² or morediscrete first regions of the resist layer, such that a like number ofdiscrete nanostructure monolayer arrays remains on the first layer.

The first layer can comprise essentially any desired material,including, but not limited to, a semiconductor or a dielectric materialsuch as an oxide (e.g., a metal oxide, silicon oxide, hafnium oxide, oralumina (Al₂O₃), or a combination of such oxides) or a nitride (e.g.,silicon nitride). The first layer is optionally treated prior todisposition of the solution, e.g., with a compound such ashexamethyldisilizane (HMDS) or a silane. Thus, for example, the firstlayer can comprise silicon oxide or silicon nitride coated with HMDS.The first layer is optionally disposed on a substrate, e.g., a substratecomprising a semiconductor (e.g., Si). In one class of embodiments, thefirst layer has a thickness of between about 1 nm and about 10 nm, e.g.,between 3 and 4 nm. The methods optionally include forming a sourceregion and a drain region in the substrate in proximity to the monolayerarray of nanostructures by, prior to step d), implanting dopant ions inthe substrate, wherein implantation damage to the substrate is repairedand the dopant is activated during step d). A gate electrode can bedisposed on the exposed resist, optionally after a dielectric layer isdisposed on the exposed resist.

The array can be an ordered or disordered array. The nanostructures areoptionally substantially spherical nanostructures or quantum dots. Thenanostructures can comprise essentially any desired material. In oneclass of embodiments, the nanostructures have a work function of about4.5 eV or higher. For example, the nanostructures can comprise a metal,e.g., palladium, platinum, nickel, or ruthenium. In some embodiments, asecond monolayer of nanostructures is disposed on the resist layer or onthe exposed resist.

Another general class of embodiments provides methods for protectingnanostructures from fusion during high temperature processing. Themethods include a) disposing the nanostructures and a silsesquioxane ona first layer, b) curing the silsesquioxane, to provide curedsilsesquioxane in which the nanostructures are embedded, and c) heatingthe first layer, the cured silsesquioxane, and its embeddednanostructures.

The nanostructures and the silsesquioxane can be disposed on the firstlayer using essentially any convenient technique. For example, the firstlayer can be spin coated with a solution comprising the silsesquioxaneand the nanostructures. The nanostructures can, but need not, form amonolayer on the first layer.

The silsesquioxane can be cured by heating, for example, by exposure toa temperature between about 300° C. and 400° C. As another example, thesilsesquioxane can be cured by exposure to ionizing radiation, e.g.,sufficient to essentially completely cure the silsesquioxane. In aparticularly useful aspect, the silsesquioxane is incompletely cured asthe nanostructures are patterned and is then subsequently further cured.

Thus, in one class of embodiments, in step b) curing the silsesquioxanecomprises b) i) exposing the silsesquioxane to ionizing radiation in apredetermined pattern, whereby the silsesquioxane in at least a firstregion is exposed and incompletely cured while the silsesquioxane in aleast a second region remains unexposed and uncured, b) ii) removing theunexposed silsesquioxane and nanostructures therein from the secondregion without removing the incompletely cured silsesquioxane and itsembedded nanostructures from the first region, and b) iii) after stepii), exposing the incompletely cured silsesquioxane in the first regionto ionizing radiation to further cure the silsesquioxane, to provide thecured silsesquioxane. In one exemplary class of embodiments, in step b)i) the silsesquioxane in the first region is exposed to about 10mJ/cm²-1 J/cm² ultraviolet light to incompletely cure the silsesquioxanein the first region, and in step b) iii) the incompletely curedsilsesquioxane in the first region is exposed to about 1 J/cm²-50 J/cm²ultraviolet light to further cure the silsesquioxane in the firstregion. Unexposed silsesquioxane and nanostructures therein can beremoved from the second region without removing the incompletely curedsilsesquioxane and its embedded nanostructures from the first region by,e.g., contacting the unexposed silsesquioxane with at least one organicsolvent. After step b) iii) and before step c), the cured silsesquioxaneis optionally exposed to a temperature between about 300° C. and 400° C.

Optionally, in step c) the first layer, the cured silsesquioxane, andits embedded nanostructures are exposed to a temperature of at leastabout 300° C. (typically, following step b), typically at least about700° C. or at least about 900° C. For example, the first layer, thecured silsesquioxane, and its embedded nanostructures can be exposed toa temperature of 950° C. or more, for example, during a high-temperatureannealing step.

As noted above, the nanostructures disposed on the first layeroptionally comprise a monolayer. In embodiments in which a monolayer ispatterned in step b), in step b) ii) at least one nanostructuremonolayer array defined by the first region remains on the first layer.

As described above, by protecting the nanostructures from fusion, themethods can maintain nanostructure density, size, size distribution,monolayer morphology, etc., during high temperature processing steps.For example, in one class of embodiments in which the nanostructureswere disposed in a monolayer, the density of nanostructures in themonolayer array after step c) is at least 90% of the density ofnanostructures in the monolayer array before step c). As describedabove, protection from fusion is increasingly important with increasingnanostructure density. Thus, the density of nanostructures in themonolayer array before step c) is optionally at least about 1×10¹°nanostructures/cm², e.g., at least about 1×10¹¹ nanostructures/cm², atleast about 1×10¹² nanostructures/cm², at least 2.5×10¹²nanostructures/cm², or at least 5×10¹² nanostructures/cm². In one classof embodiments, following step c), the monolayer array of nanostructureshas a density greater than about 1×10¹² nanostructures/cm², e.g., atleast 2.5×10¹² nanostructures/cm² or at least 5×10¹² nanostructures/cm².Optionally, density of the nanostructures in the monolayer array issubstantially uniform following step c).

In one class of embodiments, the average diameter of the nanostructuresembedded in the cured silsesquioxane after step c) is less than 110% ofthe average diameter of the nanostructures embedded in the curedsilsesquioxane before step c). In a related class of embodiments, thesize distribution of the nanostructures embedded in the curedsilsesquioxane exhibits an rms deviation of less than 20%. For example,following step c), the size distribution of the nanostructures embeddedin the cured silsesquioxane can exhibit an rms deviation of less than15%, less than 10%, or even less than 5%.

In embodiments in which the nanostructures are disposed in a monolayer,the methods optionally include disposing one or more additionalmonolayers on the monolayer. For example, in one class of embodiments,the methods include, after step b) i) and prior to step b) iii),disposing a second monolayer of nanostructures in silsesquioxane on theincompletely cured silsesquioxane.

Essentially all of the features noted for the embodiments above apply tothese embodiments as well, as relevant; for example, with respect tocomposition of the first layer, disposition of the first layer on asubstrate, composition of the substrate, nanostructure shape andcomposition, type of silsesquioxane, and the like. For example, thenanostructures are optionally substantially spherical nanostructures orquantum dots. In one class of embodiments, the nanostructures have awork function of about 4.5 eV or higher. For example, the nanostructurescan comprise a metal, e.g., palladium, platinum, nickel, or ruthenium.

Also as for the embodiments above, in embodiments in which one or moremonolayer arrays are patterned, the methods optionally includeincorporation of the array(s) into transistor(s). Thus, for example, themethods optionally include forming a source region and a drain region inthe substrate in proximity to the monolayer array of nanostructures by,prior to step c), implanting dopant ions in the substrate, whereinimplantation damage to the substrate is repaired and the dopant isactivated during step c). A gate electrode can be disposed on the curedsilsesquioxane, optionally after a dielectric layer is disposed on thecured silsesquioxane.

Another general class of embodiments provides a device that includes asubstrate and two or more nanostructure arrays disposed on thesubstrate. The substrate comprises a semiconductor, and eachnanostructure array comprises a monolayer and is disposed at apredetermined position on the substrate. For each monolayer array, thesubstrate comprises an activated source region, an activated drainregion, and a channel region between the source and drain regions andunderlying the monolayer array of nanostructures.

Suitable substrates include, but are not limited to, a quartz substrateor a silicon wafer or a portion thereof. A first layer is optionallydisposed between the monolayer arrays and the substrate. In one class ofembodiments, the first layer comprises a dielectric material and has athickness of between about 1 nm and about 10 nm, e.g., between 3 and 4nm. In some embodiments, a control dielectric layer is disposed on eachmonolayer array of nanostructures, and a gate electrode is disposed oneach control dielectric layer.

Essentially all of the features noted for the embodiments above apply tothese embodiments as well, as relevant; for example, with respect tonanostructure shape and composition, inclusion of preformednanostructures, and the like. For example, the nanostructures areoptionally substantially spherical nanostructures or quantum dots. Inone class of embodiments, the nanostructures have a work function ofabout 4.5 eV or higher. For example, the nanostructures can comprise ametal, e.g., palladium, platinum, nickel, or ruthenium. Thenanostructure arrays are optionally embedded in a cured (partially oressentially completely cured) resist, a cured silsesquioxane, silicondioxide, or the like.

The device is optionally produced by a method of the invention, andthus, as described above, can include nanostructures with a narrow sizedistribution. Accordingly, in one class of embodiments, the sizedistribution of the nanostructures in the monolayer arrays exhibits anrms deviation of less than 20%, for example, less than 15%, less than10%, or even less than 5%.

In one class of embodiments, the arrays have a high density ofnanostructures. For example, each nanostructure array optionally has adensity greater than about 1×10¹⁰ nanostructures/cm², greater than about1×10¹¹ nanostructures/cm², greater than about 1×10¹² nanostructures/cm²,at least 2.5×10¹² nanostructures/cm², at least 5×10¹²nanostructures/cm², or even greater than about 1×10¹³nanostructures/cm². Optionally, as described above, density of thenanostructures in each monolayer array is substantially uniform.

In one class of embodiments, each of the two or more monolayer arrays ofnanostructures disposed on the substrate has an additional monolayerarray (or two or more additional arrays) of nanostructures disposedthereon. A dielectric layer is optionally disposed between adjacentmonolayers.

Yet another general class of embodiments provides a memory device thatincludes at least one transistor, which transistor comprises a gate areathat is occupied by a monolayer array of nanostructures, an activatedsource region, and an activated drain region. The size distribution ofthe nanostructures in the monolayer array exhibits an rms deviation ofless than 20%. For example, the size distribution of the nanostructuresin the monolayer array can exhibit an rms deviation of less than 15%,less than 10%, or even less than 5%. Optionally, density of thenanostructures in the monolayer array is substantially uniform. The atleast one transistor can comprise two or more, 10 or more, 50 or more,100 or more, 1000 or more, 1×10⁴ or more, 1×10⁶ or more, 1×10⁹ or more,or 1×10¹² or more transistors.

Essentially all of the features noted for the embodiments above apply tothese embodiments as well, as relevant; for example, with respect tonanostructure shape and composition, inclusion of preformednanostructures, inclusion of a second monolayer array on the first, andthe like. The monolayer array optionally has a density greater thanabout 1×10¹⁰ nanostructures/cm², greater than about 1×10¹¹nanostructures/cm², greater than about 1×10¹² nanostructures/cm², atleast 2.5×10¹² nanostructures/cm², at least 5×10¹² nanostructures/cm²,or greater than about 1×10¹³ nanostructures/cm². The nanostructures inthe array are optionally embedded in a cured resist, a curedsilsesquioxane, silicon dioxide, or the like, as described above.

BRIEF DESCRIPTION OF THE DRAWINGS

FIG. 1 Panels A-C schematically illustrate formation of monolayer arraysof nanostructures on a coated first layer, where discrete regions of thefirst layer are coated.

FIG. 2 Panels A-D schematically illustrate formation of monolayer arraysof nanostructures on a coated first layer, where the coating compositionis photoactivatable and discrete regions of the first layer are exposedto light to initiate cross-linking of the composition to ligands on thenanostructures.

FIG. 3 Panel A depicts an exemplary monothiol silsesquioxane ligand,while Panel B depicts an exemplary trithiol silsesquioxane ligand. PanelC depicts an exemplary amine POSS ligand. In Panels A-C, R can be anorganic group or a hydrogen atom; for example, R can be a hydrocarbongroup, an alkyl group (e.g., a cyclic alkyl group or a short alkyl grouphaving fewer than 20 or even fewer than 10 carbon atoms), an aryl group,an alkylaryl group, an alkenyl group, or an alkynyl group. For example,in some embodiments, R is an isobutyl group, a methyl group, a hexylgroup, or a cyclopentyl group. In certain embodiments, R is a cyclohexylgroup. Panel D depicts a methacrylo silsesquioxane. Panel E depicts anacrylo silsesquioxane.

FIG. 4 schematically illustrates fabrication of a flash transistorcomprising a monolayer array of nanostructures, including use of resistto pattern the monolayer.

FIG. 5 Panels A-D schematically illustrate formation of a monolayerarray of nanostructures using a device of the invention. A side view ofthe device is schematically depicted in Panels A-C.

FIG. 6 Panels A-B schematically illustrate fabrication of devices forforming nanostructure arrays. Side views of the devices are shown.

FIG. 7 Panels A-C schematically illustrate exemplary devices of theinvention. Panel A depicts a top view of a device. Panel B presents across section of the device shown in Panel A, and outlines formation ofa monolayer array of nanostructures using the device. Panel C depicts across section of another exemplary device.

FIG. 8 presents micrographs of palladium (Panel A), ruthenium (Panel B),and nickel (Panel C) quantum dots formed by deposition of the dots in aspin-on-glass.

FIG. 9 presents micrographs of quantum dots before (Panel A) and after(Panel B) solvent annealing to improve monolayer quality.

FIG. 10 schematically illustrates patterning of a monolayer array ofnanostructures embedded in resist.

FIG. 11 presents micrographs of quantum dots patterned using methods ofthe invention.

FIG. 12 Panels A-C present micrographs of ruthenium quantum dots insilsesquioxane after exposure to 950° C., where the dots were notprotected by previous curing of the silsesquioxane (Panel A) or wereprotected by previous UV curing of the silsesquioxane for 15 minutes(Panel B) or 100 minutes (Panel C).

FIG. 13 schematically illustrates fabrication of a flash transistorcomprising a monolayer array of nanostructures, including use of resistto pattern and protect the monolayer.

Figures are not necessarily to scale.

DEFINITIONS

Unless defined otherwise, all technical and scientific terms used hereinhave the same meaning as commonly understood by one of ordinary skill inthe art to which the invention pertains. The following definitionssupplement those in the art and are directed to the current applicationand are not to be imputed to any related or unrelated case, e.g., to anycommonly owned patent or application. Although any methods and materialssimilar or equivalent to those described herein can be used in thepractice for testing of the present invention, the preferred materialsand methods are described herein. Accordingly, the terminology usedherein is for the purpose of describing particular embodiments only, andis not intended to be limiting.

As used in this specification and the appended claims, the singularforms “a,” “an” and “the” include plural referents unless the contextclearly dictates otherwise. Thus, for example, reference to “ananostructure” includes a plurality of such nanostructures, and thelike.

The term “about” as used herein indicates the value of a given quantityvaries by +/−10% of the value, or optionally +/−5% of the value, or insome embodiments, by +/−1% of the value so described.

A “nanostructure” is a structure having at least one region orcharacteristic dimension with a dimension of less than about 500 nm,e.g., less than about 200 nm, less than about 100 nm, less than about 50nm, or even less than about 20 nm. Typically, the region orcharacteristic dimension will be along the smallest axis of thestructure. Examples of such structures include nanowires, nanorods,nanotubes, branched nanostructures, nanotetrapods, tripods, bipods,nanocrystals, nanodots, quantum dots, nanoparticles, and the like.Nanostructures can be, e.g., substantially crystalline, substantiallymonocrystalline, polycrystalline, amorphous, or a combination thereof.In one aspect, each of the three dimensions of the nanostructure has adimension of less than about 500 nm, e.g., less than about 200 nm, lessthan about 100 nm, less than about 50 nm, or even less than about 20 nm.

An “aspect ratio” is the length of a first axis of a nanostructuredivided by the average of the lengths of the second and third axes ofthe nanostructure, where the second and third axes are the two axeswhose lengths are most nearly equal each other. For example, the aspectratio for a perfect rod would be the length of its long axis divided bythe diameter of a cross-section perpendicular to (normal to) the longaxis.

As used herein, the “diameter” of a nanostructure refers to the diameterof a cross-section normal to a first axis of the nanostructure, wherethe first axis has the greatest difference in length with respect to thesecond and third axes (the second and third axes are the two axes whoselengths most nearly equal each other). The first axis is not necessarilythe longest axis of the nanostructure; e.g., for a disk-shapednanostructure, the cross-section would be a substantially circularcross-section normal to the short longitudinal axis of the disk. Wherethe cross-section is not circular, the diameter is the average of themajor and minor axes of that cross-section. For an elongated or highaspect ratio nanostructure, such as a nanowire or nanorod, a diameter istypically measured across a cross-section perpendicular to the longestaxis of the nanowire or nanorod. For spherical nanostructures such asquantum dots, the diameter is measured from one side to the otherthrough the center of the sphere.

The terms “crystalline” or “substantially crystalline,” when used withrespect to nanostructures, refer to the fact that the nanostructurestypically exhibit long-range ordering across one or more dimensions ofthe structure. It will be understood by one of skill in the art that theterm “long range ordering” will depend on the absolute size of thespecific nanostructures, as ordering for a single crystal cannot extendbeyond the boundaries of the crystal. In this case, “long-rangeordering” will mean substantial order across at least the majority ofthe dimension of the nanostructure. In some instances, a nanostructurecan bear an oxide or other coating, or can be comprised of a core and atleast one shell. In such instances it will be appreciated that theoxide, shell(s), or other coating need not exhibit such ordering (e.g.,it can be amorphous, polycrystalline, or otherwise). In such instances,the phrase “crystalline,” “substantially crystalline,” “substantiallymonocrystalline,” or “monocrystalline” refers to the central core of thenanostructure (excluding the coating layers or shells). The terms“crystalline” or “substantially crystalline” as used herein are intendedto also encompass structures comprising various defects, stackingfaults, atomic substitutions, and the like, as long as the structureexhibits substantial long range ordering (e.g., order over at leastabout 80% of the length of at least one axis of the nanostructure or itscore). In addition, it will be appreciated that the interface between acore and the outside of a nanostructure or between a core and anadjacent shell or between a shell and a second adjacent shell maycontain non-crystalline regions and may even be amorphous. This does notprevent the nanostructure from being crystalline or substantiallycrystalline as defined herein.

The term “monocrystalline” when used with respect to a nanostructureindicates that the nanostructure is substantially crystalline andcomprises substantially a single crystal. When used with respect to ananostructure heterostructure comprising a core and one or more shells,“monocrystalline” indicates that the core is substantially crystallineand comprises substantially a single crystal.

A “nanocrystal” is a nanostructure that is substantiallymonocrystalline. A nanocrystal thus has at least one region orcharacteristic dimension with a dimension of less than about 500 nm,e.g., less than about 200 nm, less than about 100 nm, less than about 50nm, or even less than about 20 nm. The term “nanocrystal” is intended toencompass substantially monocrystalline nanostructures comprisingvarious defects, stacking faults, atomic substitutions, and the like, aswell as substantially monocrystalline nanostructures without suchdefects, faults, or substitutions. In the case of nanocrystalheterostructures comprising a core and one or more shells, the core ofthe nanocrystal is typically substantially monocrystalline, but theshell(s) need not be. In one aspect, each of the three dimensions of thenanocrystal has a dimension of less than about 500 nm, e.g., less thanabout 200 nm, less than about 100 nm, less than about 50 nm, or evenless than about 20 nm. Examples of nanocrystals include, but are notlimited to, substantially spherical nanocrystals, branched nanocrystals,and substantially monocrystalline nanowires, nanorods, nanodots, quantumdots, nanotetrapods, tripods, bipods, and branched tetrapods (e.g.,inorganic dendrimers).

A “substantially spherical nanostructure” is a nanostructure with anaspect ratio between about 0.8 and about 1.2. For example, a“substantially spherical nanocrystal” is a nanocrystal with an aspectratio between about 0.8 and about 1.2.

A “nanostructure array” is an assemblage of nanostructures. Theassemblage can be spatially ordered (an “ordered array”) or disordered(a “disordered array”). In a “monolayer array” of nanostructures, theassemblage of nanostructures comprises a monolayer.

A variety of additional terms are defined or otherwise characterizedherein.

DETAILED DESCRIPTION

In one aspect, the invention provides methods for forming nanostructurearrays, e.g., ordered or disordered monolayer arrays of nanostructures.The arrays are optionally formed at predetermined positions and/or havepredetermined dimensions. Devices related to the methods are alsoprovided, as are devices including nanostructure arrays. For example, inone aspect, the invention provides memory devices including smallmonolayer arrays of nanostructures.

Monolayer Formation on Chemical Coatings

A surface on which a nanostructure array is to be formed can be coatedwith a chemical composition, e.g., a composition having a higheraffinity for the nanostructures than the surface itself does. Such acoating can, e.g., facilitate adhesion of the nanostructures to thesurface and can thus facilitate formation of the monolayer.

Thus, one general class of embodiments provides methods for forming ananostructure array. In the methods, a first layer is provided andcoated with a composition comprising a nanostructure association group,to provide a coated first layer. A population of nanostructures isdeposited on the coated first layer, whereby the nanostructuresassociate with the nanostructure association group. Any nanostructureswhich are not associated with the nanostructure association group areremoved, whereby a monolayer array of nanostructures remains associatedwith the coated first layer.

The first layer can comprise essentially any desired material, chosen,e.g., based on the use to which the resulting monolayer array ofnanostructures is to be put (e.g., a conductive material, anonconductive material, a semiconductor, or the like). The first layeris optionally disposed or deposited on a substrate, which can similarlycomprise essentially any desired material, depending, e.g., on thedesired use of the nanostructure array. Suitable substrates include, butare not limited to: a uniform substrate, e.g., a wafer of solidmaterial, such as silicon or other semiconductor material, glass,quartz, polymerics, etc.; a large rigid sheet of solid material, e.g.,glass, quartz, plastics such as polycarbonate, polystyrene, etc.; aflexible substrate, such as a roll of plastic such as polyolefin,polyamide, and others; or a transparent substrate. Combinations of thesefeatures can be employed. The substrate optionally includes othercompositional or structural elements that are part of an ultimatelydesired device. Particular examples of such elements include electricalcircuit elements such as electrical contacts, other wires or conductivepaths, including nanowires or other nanoscale conducting elements,optical and/or optoelectrical elements (e.g., lasers, LEDs, etc.), andstructural elements (e.g., microcantilevers, pits, wells, posts, etc.).

For example, in embodiments in which the monolayer array ofnanostructures is to be incorporated into a flash transistor or memorydevice, the first layer comprises a dielectric material, such as anoxide (e.g., a metal oxide, silicon oxide, hafnium oxide, or alumina(Al₂O₃), or a combination of such oxides), a nitride (e.g., Si₃N₄), aninsulating polymer, or another nonconductive material. In this class ofembodiments, the first layer (which serves as a tunnel dielectric layerin these embodiments) is preferably thin (e.g., has a thickness ofbetween about 1 nm and about 10 nm, e.g., between 3 and 4 nm), and isdisposed on a substrate that comprises a semiconductor. Preferred tunneldielectrics are described in Chen U.S. Patent Publication No.2008/0150009, which is herein incorporated by reference in its entirety.The substrate typically includes a source region, a drain region, and achannel region between the source and drain regions and underlying themonolayer array of nanostructures, and the methods include disposing acontrol dielectric layer on the monolayer array of nanostructures anddisposing a gate electrode on the control dielectric layer, thusincorporating the nanostructure array into a transistor. The controldielectric layer comprises a dielectric material, for example, an oxide(e.g., a metal oxide, SiO₂, or Al₂O₃, or a combination of such oxides),an insulating polymer, or another nonconductive material. Preferredcontrol dielectrics are described in Chen U.S. Patent Publication No.2008/0150009 (supra), and preferred gate electrode design is describedin Duan et al. U.S. Pat. No. 8,030,161, each of which is hereinincorporated by reference in its entirety.

The methods can be used to form multiple nanostructure arrays on thesame surface. Thus, in one class of embodiments, two or more discreteregions of the first layer are coated with the composition. Each regionoccupies a predetermined position on the first layer (which can, e.g.,correspond to a predetermined position on a substrate on which the firstlayer is disposed). Two or more discrete monolayer arrays ofnanostructures thus remain associated with the coated first layer afterdeposition of the population of nanostructures on the coated regions ofthe first layer and removal of nanostructures not associated with thenanostructure association group. Essentially any number of nanostructurearrays can be produced in this manner. For example, 10 or more, 50 ormore, 100 or more, 1000 or more, 1×10⁴ or more, 1×10⁶ or more, 1×10⁹ ormore, 1×10¹⁰ or more, 1×10¹¹ or more, or 1×10¹² or more discrete regionsof the first layer can be coated with the composition, whereby 10 ormore, 50 or more, 100 or more, 1000 or more, 1×10⁴ or more, 1×10⁶ ormore, 1×10⁹ or more, 1×10¹⁰ or more, 1×10¹¹ or more, or 1×10¹² or morediscrete monolayer nanostructure arrays are formed at predeterminedpositions on the first layer.

The regions can be of essentially any desired size. For example, eachregion (and thus each resulting monolayer array of nanostructures) canhave an area of about 10⁴ μm² or less, about 10³ μm² or less, about 10²μm² or less, about 10 μm² or less, about 1 μm² or less, about 10⁵ nm² orless, about 10⁴ nm² or less, or even about 4225 nm² or less, about 2025nm² or less, about 1225 nm² or less, about 625 nm² or less, or about 324nm² or less. It will be evident that each of the resulting arrays can,if desired, be incorporated into a transistor or other device.

Techniques useful for coating discrete regions of the first layer havebeen described in the art. For example, the first layer can be coatedwith resist (e.g., photoresist), which is exposed and developed in thedesired pattern to uncover the desired regions of the first layer, whichare then coated with the composition. As another example, the firstlayer can be coated with the composition, then with resist which isexposed and developed in the inverse of the desired pattern. Compositionnot protected by the resist is removed, and the remaining resist isremoved to leave the composition in the desired regions. As yet anotherexample, the composition can simply be printed on the first layer indesired regions. In another class of embodiments, the monolayer isformed and then patterned, e.g., using resist as described below in thesection entitled “Patterning monolayers using resist.”

As noted, the composition used to coat the first layer comprises ananostructure association group (e.g., a chemical group that caninteract, covalently or noncovalently, with a surface of a nanostructureand/or with a ligand coating a surface of a nanostructure). A largenumber of suitable groups are known in the art and can be adapted to thepractice of the present invention. Exemplary nanostructure associationgroups include, but are not limited to, thiol, amine, alcohol,phosphonyl, carboxyl, boronyl, fluorine or other noncarbon heteroatom,phosphinyl, alkyl, aryl, and like groups.

In one class of embodiments, the composition comprises a silane. Forexample, the silane can be an organosilane, e.g., a trichlorosilane,trimethoxysilane, or triethoxysilane. As another example, the silane caninclude a structure having the formula [X₃Si-spacer-nanostructureassociation group(s)] where X is a Cl, OR, alkyl, aryl, otherhydrocarbon, heteroatom, or a combination of these groups, and where thespacer is an alkyl, aryl and/or heteroatom combination. The silane canreact with free hydroxyl groups on the surface of a silicon oxide firstlayer, for example, forming a monolayer coating on the first layer.

In one aspect, the nanostructure association group interacts with asurface of the nanostructures. In one exemplary class of embodiments,the nanostructure association group comprises a thiol group. The coatedfirst layer can thus comprise, e.g., a self-assembled monolayercomprising a thiol compound. The composition can comprise, for example,a mercaptoalkyltrichlorosilane, a mercaptoalkyltrimethoxysilane, or amercaptoalkyltriethoxysilane, e.g., in which the alkyl group comprisesbetween 3 and 18 carbons (e.g., 12-mercaptododecyltrimethoxysilane). Thecomposition optionally comprises a mixture of two or more differentcompounds. For example, the composition can include a mixture of a longchain mercaptosilane (e.g., a mercaptoalkyltrichlorosilane, amercaptoalkyltrimethoxysilane, or a mercaptoalkyltriethoxysilane, wherethe alkyl group comprises between 8 and 18 carbons) and a short chainmercaptosilane (e.g., a mercaptoalkyltrichlorosilane, amercaptoalkyltrimethoxysilane, or a mercaptoalkyltriethoxysilane, wherethe alkyl group comprises 8 or fewer carbons), where the alkyl group inthe long chain mercaptosilane comprises at least one more carbon thandoes the alkyl group in the short chain mercaptosilane. In this example,the ratio of the long and short chain mercaptosilanes can be varied totailor the surface presented to the nanostructures. For example, thelong and short chain mercaptosilanes can be present at a molar ratio ofbetween about 1:10 and about 1:10,000 long chain mercaptosilane to shortchain mercaptosilane (e.g., a molar ratio of about 1:100 or 1:1000). Asanother example, the composition can include a mixture of a long chainmercaptosilane and a short chain silane which need not comprise ananostructure association group (e.g., an alkyltrichlorosilane,alkyltrimethoxysilane, or alkyltriethoxysilane, where the alkyl groupcomprises 8 or fewer carbons).

The nanostructures are optionally associated with a surfactant or othersurface ligand. In one class of embodiments, each of the nanostructurescomprises a coating comprising a ligand associated with a surface of thenanostructure, for example, a silsesquioxane ligand such as thosedescribed in Whiteford et al. U.S. Pat. No. 7,267,875 or illustrated inFIG. 3 Panels A-C. The ligands optionally control spacing betweenadjacent nanostructures in an array. The nanostructure association groupcan displace the ligand and/or can intercalate between adjacent ligandmolecules to reach the surface of the nanostructures.

An exemplary embodiment is schematically illustrated in FIG. 1. In thisexample, first layer 103 (e.g., a layer of SiO₂) is disposed onsubstrate 120 (e.g., a silicon substrate). The first layer as depictedis continuously distributed across the substrate, but it will be evidentthat the first layer can optionally instead be disposed in multiplediscrete regions on the substrate. The first layer is coated withcomposition 104 (e.g., a mixture of long and short chainmercaptosilanes) including nanostructure association group 105 (e.g., athiol group), to form coated first layer 102 in discrete regions 119. Apopulation of nanostructures 110 (e.g., Pd quantum dots) coated withligand 111 (e.g., a silsesquioxane ligand) is deposited on the coatedfirst layer, e.g., by spin coating (Panel A). Nanostructures associatewith the nanostructure association group, which intercalates among theligand coating the nanostructures, and form slightly more than amonolayer on the first layer (Panel B). Nanostructures that are notassociated with the nanostructure association group are removed (e.g.,by washing with a solvent) to leave monolayer arrays 109 ofnanostructures associated with the coated first layer (Panel C).

Instead of (or in addition to) displacing or intercalating with theligand on the nanostructures to interact with the nanostructure surface,the nanostructure association group can interact with the ligand. Thus,in one aspect, each of the nanostructures comprises a coating comprisinga ligand associated with a surface of the nanostructure, and thenanostructure association group interacts with the ligand. In someembodiments, the ligand comprises a silsesquioxane. Exemplary ligandsinclude, but are not limited to, those described in U.S. ProvisionalPatent Application Ser. No. 60/632,570 (supra) or illustrated in FIG. 3Panels A-C.

The interaction between the ligand and the nanostructure associationgroup can be covalent or noncovalent. Thus, in one class of embodiments,the interaction is noncovalent. The composition can comprise, forexample, 3-aminopropyltriethoxysilane (APTES), dodecyltrichlorosilane,octadecyltrichlorosilane (OTS), dodecyltriethoxysilane,octadecyltriethoxysilane, or any of a number of similar compounds. Asnoted above, the silanes can, e.g., bind to free hydroxyl groups on thesurface of an SiO₂ first layer. The dodecyl and octadecyl groups providea hydrophobic surface, e.g., for interaction with a hydrophobic ligandon the nanostructures, while APTES provides a polar surface, e.g., forinteraction with a ligand that can hydrogen bond with the APTES aminogroups.

In another class of embodiments, the nanostructure association groupforms a covalent bond with the ligand. The composition is optionallyphotoactivatable, such that the covalent bond between the ligand and thenanostructure association group is formed only upon exposure to light.In such embodiments, the methods include exposing one or more discreteregions of the coated first layer, each of which occupies apredetermined position on the coated first layer, to light.

Essentially any number of nanostructure arrays can be produced in thismanner. For example, two or more, 10 or more, 50 or more, 100 or more,1000 or more, 1×10⁴ or more, 1×10⁶ or more, 1×10⁹ or more, 1×10¹⁰ ormore, 1×10¹¹ or more, or 1×10¹² or more discrete regions of the coatedfirst layer can be exposed to the light, resulting in formation of alike number of discrete nanostructure monolayer arrays at predeterminedpositions on the first layer (and thus, at predetermined positions onany substrate on which the first layer is disposed). Similarly, theregions can be of essentially any desired size. For example, each region(and thus each resulting monolayer array of nanostructures) can have anarea of about 10⁴ μm² or less, about 10³ μm² or less, about 10² μm² orless, about 10 μm² or less, about 1 μm² or less, about 10⁵ nm² or less,about 10⁴ nm² or less, or even about 4225 nm² or less, about 2025 nm² orless, about 1225 nm² or less, about 625 nm² or less, or about 324 nm² orless. It will be evident that each of the resulting arrays can, ifdesired, be incorporated into a transistor or other device. Using aphotoactivatable composition thus provides a convenient means ofpatterning, such that a desired number, size, and/or shape of monolayernanostructure array(s) can be produced.

A large number of photoactivatable compounds are known in the art andcan be adapted to the practice of the present invention. For example,the composition can include a phenyl azide group, which whenphotoactivated can form a covalent bond with, e.g., a silsesquioxaneligand comprising a coating associated with a surface of thenanostructures. Exemplary photoactivatable compositions include, but arenot limited to, compounds comprising an aryl azide group (e.g., a phenylazide, hydroxyphenyl azide, or nitrophenyl azide group), a psoralen, ora diene.

The composition can be applied to form the coating in one or more steps.For example, in certain embodiments, coating the first layer with thecomposition involves coating the first layer with a first compound andthen coating the first layer with a second compound which interacts withthe first compound and which includes the nanostructure associationgroup. For example, the first layer (e.g., an SiO₂ first layer) can becoated with 3-aminopropyltriethoxysilane (APTES) as the first compoundand then with N-5-azido-2-nitrobenzoyloxysuccinimide (ANB-NOS) as thesecond compound. (ANB-NOS has an amine-reactive N-hydroxysuccinimideester group, which reacts with the APTES amino groups, and a nitrophenylazide group, which can be photolyzed, e.g., at 320-350 nm.)

An exemplary embodiment is schematically illustrated in FIG. 2. In thisexample, first layer 203 (e.g., a layer of SiO₂) is disposed onsubstrate 220 (e.g., a silicon substrate). The first layer is coatedwith composition 204 (e.g., APTES and ANB-NOS), which includesphotoactivatable nanostructure association group 205 (e.g., a phenylazide group), to form coated first layer 202 (Panel A). A population ofnanostructures 210 (e.g., Pd quantum dots) coated with ligand 211 (e.g.,a silsesquioxane ligand) is deposited on the coated first layer, e.g.,by spin coating to form slightly more than a monolayer (Panel B).Discrete regions 219 of the coated first layer are exposed to light 230,while the remainder of the coated first layer is protected from exposureto the light by mask 231 (Panel C). Nanostructures that are notcovalently bonded to the nanostructure association group are removed(e.g., by washing with a solvent, e.g., hexane) to leave monolayerarrays 209 of nanostructures associated with the coated first layer(Panel D).

In one class of embodiments, the population of nanostructures isdeposited on the coated first layer by depositing a solution comprisingthe nanostructures dispersed in at least one solvent on the coated firstlayer. The solution of nanostructures can be deposited by essentiallyany convenient technique, for example, spin coating, dip coating,soaking, spraying, or similar techniques. The solvent can, but need notbe, partially or completely removed from the deposited nanostructures,e.g., by evaporation. Any nanostructures which are not associated withthe nanostructure association group can be conveniently removed, e.g.,by washing with at least one solvent.

In one aspect, the monolayer array (or each of multiple arrays) ofnanostructures formed by the methods comprises an ordered array, e.g., ahexagonal-close packed monolayer array comprising substantiallyspherical nanocrystals or a square array comprising cubic nanocrystals.For many applications, however, an ordered array is not required. Forexample, for an array for use in a memory device, the nanostructuresneed not be ordered in the array as long as they achieve sufficientdensity in a disordered array. Thus, in another aspect, the monolayerarray of nanostructures comprises a disordered array.

In one class of embodiments, the array (or each of multiple arraysproduced by the methods) has a high density of nanostructures. Forexample, the monolayer array of nanostructures optionally has a densitygreater than about 1×10¹⁰ nanostructures/cm², greater than about 1×10¹¹nanostructures/cm², greater than about 1×10¹² nanostructures/cm², oreven greater than about 1×10¹³ nanostructures/cm².

In one class of embodiments, the nanostructures comprise substantiallyspherical nanostructures or quantum dots. The nanostructures cancomprise essentially any desired material, chosen, e.g., based on theuse to which the resulting monolayer array of nanostructures is to beput. For example, the nanostructures can comprise a conductive material,a nonconductive material, a semiconductor, and/or the like. In oneaspect, the nanostructures have a work function of about 4.5 eV orhigher. Such nanostructures are useful, for example, in fabrication ofmemory devices, where if the work function of the nanostructures is notsufficiently high, electrons stored in the nanostructures tend to travelback across the tunnel dielectric layer, resulting in memory loss. Thus,the nanostructures (e.g., the substantially spherical nanostructures orquantum dots) optionally comprise materials such as palladium (Pd),iridium (Ir), nickel (Ni), platinum (Pt), gold (Au), ruthenium (Ru),cobalt (Co), tungsten (W), tellurium (Te), iron platinum alloy (FePt),or the like. Nanostructures are described in greater detail below in thesection entitled “Nanostructures”.

Devices produced by or useful in practicing the methods of the inventionare also a feature of the invention. Thus, another general class ofembodiments provides a device including a coated first layer and amonolayer array of nanostructures disposed on the coated first layer.The coated first layer includes a first layer coated with a compositioncomprising a nanostructure association group, and the nanostructures areassociated with the nanostructure association group.

Essentially all of the features noted for the methods above apply tothese embodiments as well, as relevant; for example, with respect tocomposition of the first layer, substrate, composition used to coat thefirst layer, nanostructure association group, and nanostructures. It isworth noting that the monolayer array of nanostructures can comprise anordered array or a disordered array, and that the coated first layeroptionally comprises two or more discrete regions, each of whichoccupies a predetermined position (so the device optionally includes twoor more monolayer arrays of nanostructures disposed on the coated firstlayer). It is also worth noting that the device optionally comprises aflash transistor (floating gate memory MOSFET) or memory device. Thus,in certain embodiments, the first layer comprises a dielectric material,such as an oxide (e.g., a metal oxide, silicon oxide, hafnium oxide, oralumina (Al₂O₃)), a nitride, an insulating polymer, or anothernonconductive material. In this class of embodiments, the first layer(which serves as a tunnel dielectric layer) is preferably thin (e.g.,has a thickness of between about 1 nm and about 10 nm, e.g., between 3and 4 nm), and is disposed on a substrate that comprises a semiconductor(e.g., a Si substrate). The substrate typically includes a sourceregion, a drain region, and a channel region between the source anddrain regions and underlying the monolayer array of nanostructures. Acontrol dielectric layer is disposed on the monolayer array ofnanostructures, and a gate electrode is disposed on the controldielectric layer. The control dielectric layer comprises a dielectricmaterial, e.g., an oxide (e.g., a metal oxide, SiO₂, or Al₂O₃), aninsulating polymer, or another nonconductive material. The electrodescan comprise essentially any suitable material(s). For example, the gateelectrode can comprise polysilicon, a metal silicide (e.g., nickelsilicide or tungsten silicide), ruthenium, ruthenium oxide, or Cr/Au.Similarly, the source and drain electrodes optionally comprise a metalsilicide (e.g., nickel silicide or tungsten silicide) or any of variousbarrier metals or metal nitrides such as TiN, connecting to other metalssuch as copper or aluminum.

An exemplary embodiment is schematically illustrated in FIG. 1 Panel C.In this example, device 101 includes coated first layer 102 andmonolayer arrays 109 of nanostructures 110 disposed on the coated firstlayer in discrete regions 119. Coated first layer 102 includes firstlayer 103 coated with composition 104 including nanostructureassociation group 105. The first layer is disposed on substrate 120.

A related exemplary embodiment is schematically illustrated in FIG. 2Panel D. In this example, device 201 includes coated first layer 202 andmonolayer arrays 209 of nanostructures 210 disposed on the coated firstlayer in discrete regions 219. Coated first layer 202 includes firstlayer 203 coated with composition 204 including nanostructureassociation group 205. The first layer is disposed on substrate 220. Inthis embodiment, nanostructure association group 205 is covalentlybonded to ligand 211 on the nano structures.

Monolayer Formation in Spin-on-Dielectrics

As noted above, nanostructure monolayers are desirable for a number ofapplications. For example, formation of quantum dot monolayers on tunneloxides is desirable for production of nanocrystal flash memory devices.Because the performance of nanocrystal based flash memory devices (orother nanostructure-based devices) can be determined at least in part byvariations in nanostructure density, high density monolayers with lownanostructure density variations are desired. However, since imperfectsize distribution of the nanodots affects coherent length ofself-assembly, simply coating a substrate with dots (e.g., a substratewhose surface is not modified with a composition that includes ananostructure association group and where the dots are not dispersed ina matrix material, etc.) typically results in localized dot assemblieswith grain boundary formed among them. Since the coherent self-assemblylength depends on the size distribution of the dots, the quality of theassembly process has been limited by the size distribution of the dotsand it has been challenging to improve the quality of the resultingassemblies. Solution phase chemistry usually provides size distributionsof less than 10%, while the conventional CVD and PVD approaches providegrain distributions of about 20% to 25%.

One aspect of the invention provides methods that facilitate randomizedassembly of nanostructures (e.g., quantum dots) without grain boundaryformation by using spin-on-dielectric materials. The nanostructures aredispersed well in a solution in the presence of a spin-on-dielectric(e.g., spin-on-glass) material. When the nanostructure solution is spunonto a substrate, the nanostructures form a randomized monolayerassembly in the spin-on-dielectric material. The spin-on-dielectricmaterial forms a matrix on the substrate after the coating process; thenanostructures are randomly distributed in the matrix. The nanostructuredensity in the resulting array is controlled by their concentration inthe solution. Variation in nanostructure density across the resultingmonolayer is minimal.

Accordingly, one general class of embodiments provides methods forforming a nanostructure array. In the methods, a first layer isprovided, as are nanostructures dispersed in a solution comprising aliquid form of a spin-on-dielectric. The solution is disposed on thefirst layer, whereby the nanostructures form a monolayer array on thefirst layer. The liquid form of the spin-on-dielectric is then cured toprovide a solid form of the spin-on-dielectric. The monolayer array ofnanostructures is embedded in the resulting solid spin-on-dielectricmatrix.

Suitable materials for the first layer have been described above;examples include, but are not limited to, a semiconductor or adielectric material such as an oxide (e.g., a metal oxide, siliconoxide, hafnium oxide, or alumina (Al₂O₃), or a combination of suchoxides) or a nitride (e.g., silicon nitride). The first layer isoptionally treated prior to disposition of the solution. For example,the first layer can be coated with hexamethyldisilizane (HMDS) or asilane before the solution is disposed on it. Thus, for example, thefirst layer can comprise silicon oxide or silicon nitride coated withHMDS. The first layer is optionally disposed on a substrate, e.g., asubstrate comprising a semiconductor. In one class of embodiments, thefirst layer has a thickness of between about 1 nm and about 10 nm, e.g.,between 3 and 4 nm. The substrate can include a source region, a drainregion, and a channel region between the source and drain regions andunderlying the monolayer array of nanostructures, and the methodsinclude disposing a gate electrode on the solid form of thespin-on-dielectric material. Optionally, the thickness of the controldielectric is increased by disposing a dielectric layer on the solidform of the spin-on-dielectric, prior to disposing the gate electrode onthe solid form of the spin-on-dielectric material. As noted above,preferred tunnel and control dielectrics and gate electrodes aredescribed in Chen U.S. Patent Publication No. 2008/0150009 and Duan etal. U.S. Pat. No. 8,030,161, respectively.

The solution including the nanostructures and the liquidspin-on-dielectric can be disposed on the first layer by essentially anyconvenient technique. For example, the first layer can be spin coatedwith the solution.

A large number of spin-on-dielectric materials are known in the art andcan be adapted to the methods. As just a few examples, the solid form ofthe spin-on-dielectric can comprise silicon oxide, aluminum oxide,hafnium oxide (e.g., HfO₂), lanthanum oxide (e.g., La₂O₃), or tantalumoxide (e.g., Ta₂O₅). Similarly, the liquid form of thespin-on-dielectric can comprise aluminum i-propoxide (Al i-propoxide),tri-methyl aluminum, tri-ethyl aluminum, hafnium t-butoxide (Hft-butoxide), hafnium ethoxide (Hf ethoxide), tetrabenzyl hafnium(tetrabenzyl Hf), tris(cyclopentadienyl)lanthanum,tris(i-propylcyclopentadienyl)lanthanum,pentakis(dimethylamino)tantalum, tantalum methoxide (Ta methoxide), ortantalum ethoxide (Ta ethoxide). As noted herein, the solid form of thespin-on-dielectric optionally serves as a diffusion barrier.

In one class of embodiments, the spin-on-dielectric is a spin-on-glass.The liquid form of the spin-on-glass can comprise a silicon compoundthat forms a silicon oxide (e.g., SiO₂) after curing. For example, theliquid form of the spin-on-glass can include a silsesquioxane, e.g.,mercapto-propyl-cyclohexyl polyhedral oligomeric silsesquioxane (seeFIG. 3 Panel A, where R is a cyclohexyl group), hydrogen silsesquioxane,methyl silsesquioxane, octavinyl dimethyl silyl silsesquioxane,octasilane silsesquioxane, octavinyl-T8 silsesquioxane,aminopropylcyclohexyl polyhedral oligomeric silsesquioxane(aminopropylcyclohexyl POSS, see FIG. 3 Panel C, where R is a cyclohexylgroup; commercially available from Hybrid Plastics, Inc.), acrylosilsesquioxane (e.g., an acrylo POSS® cage mixture commerciallyavailable from Hybrid Plastics, Inc., that includes(C₆H₉O₂)_(n)(SiO_(1.5))_(n) where n=8, 10, 12; n=8 is shown in FIG. 3Panel E), or methacrylo silsesquioxane (e.g., a methacryl POSS® cagemixture commercially available from Hybrid Plastics, Inc., that includes(C₇H₁₁O₂)_(n)(SiO_(1.5))_(n) where n=8, 10, 12; n=8 is shown in FIG. 3Panel D), or a combination thereof (e.g., a combination ofsilsesquioxanes with and without a nanostructure binding moiety that canbind to the surface of the nanostructures, e.g., a mixture ofmercapto-propyl-cyclohexyl POSS and hydrogen silsesquioxane). A varietyof such silsesquioxanes are known in the art, and a number arecommercially available, e.g., from Gelest, Inc. Other types ofspin-on-glass materials can also be used. Preferred spin-on-glass orspin-on-dielectric materials are ones which dissolve well in the solventfor the nanostructures and produce good wetting behavior on the relevantsurface (e.g., on an HMDS modified tunnel oxide layer).

The spin-on-dielectric material can be cured as is known in the art, forexample, by UV, electron beam, heat, or the like. In one class ofembodiments, the liquid form of the spin-on-dielectric comprises aphotopolymerizable compound (e.g., hydrogen silsesquioxane oroctavinyl-T8 silsesquioxane or another photopolymerizable silsesquioxaneor silicate). Use of a photopolymerizable spin-on-dielectric facilitatespatterning of the monolayer array, as described in greater detail belowin the section entitled “Patterning monolayers using resist.” In brief,to pattern the array, a predetermined pattern is exposed to light tocure the spin-on-dielectric, and uncured material along with itsembedded nanostructures is removed.

Thus, in one class of embodiments, at least a first region of the firstlayer and the solution disposed thereon are exposed to light of anappropriate wavelength, thereby curing the spin-on-dielectric in thefirst region. Simultaneously, at least a second region of the firstlayer and the solution disposed thereon are protected from the light,whereby the spin-on-dielectric in the second region remains uncured. Theuncured spin-on-dielectric and the nanostructures therein are thenremoved from the first layer without removing the curedspin-on-dielectric and the nanostructures therein, leaving one or moremonolayer arrays on the first layer. The position and size of thearray(s) in the cured spin-on-dielectric matrix correspond to that ofthe first region(s).

The methods can be used to produce essentially any number of monolayerarrays. For example, two or more, 10 or more, 50 or more, 100 or more,1000 or more, 1×10⁴ or more, 1×10⁶ or more, 1×10⁹ or more, or even1×10¹² or more discrete regions of the first layer and the solutiondisposed thereon can be exposed to the light, such that a like number ofdiscrete nanostructure monolayer arrays remains on the first layer.

Similarly, if such patterning is desired when the spin-on-dielectric isnot conveniently photopolymerizable, a photoresist (e.g., anywell-established photoresist) can be included in the solution with thenanostructures and the liquid form of the spin-on-dielectric. Thepercentage of the various components are adjusted as desired, e.g., toprovide adequate photo-curing of the matrix and a good dielectric aftercuring.

The monolayer array of nanostructures is typically a disordered array.The array (or each of multiple arrays) produced by the methodsoptionally has a high density of nanostructures. For example, themonolayer array of nanostructures optionally has a density greater thanabout 1×10¹⁰ nanostructures/cm², greater than about 1×10¹¹nanostructures/cm², greater than about 1×10¹² nanostructures/cm², oreven greater than about 1×10¹³ nanostructures/cm². As noted, variationin the density of the nanostructures across the array (or over largeareas of the array, e.g., areas 2-3 micrometers on a side) is preferablylow. For example, variation in density of the nanostructures in themonolayer array can be less than 10% across the monolayer, e.g., lessthan 5%.

Essentially all of the features noted for the embodiments above apply tothese embodiments as well, as relevant; for example, with respect todisposition of the first layer on a substrate, composition of thesubstrate, incorporation of the array(s) into transistor(s),nanostructure shape and composition, nanostructure ligands, size of thearray(s), and the like. For example, the nanostructures are optionallysubstantially spherical nanostructures or quantum dots. Thenanostructures can comprise essentially any desired material. In oneclass of embodiments, the nanostructures have a work function of about4.5 eV or higher. For example, the nanostructures can comprisepalladium, platinum, nickel, or ruthenium.

Monolayer formation of Pd, Ru, and Ni quantum dots is illustrated inFIG. 8 Panels A-C, respectively. In these examples, the substrate wascoated with HMDS, and mercapto-propyl-cyclohexyl polyhedral oligomericsilsesquioxane (3.5 mg/ml in chlorobenzene or xylene) was used as thespin-on-glass material. In these examples, a silicon nitride membranewas used as the substrate; other exemplary substrates include, e.g., anSiO₂ wafer or oxynitride substrate. The silsesquioxane was cured in anO₂, CDA environment, by ramping to 300-400° C. and dwelling at the hightemperature for 5-30 minutes.

As noted, devices produced by or useful in practicing the methods of theinvention are also a feature of the invention. Thus, another generalclass of embodiments provides a device including a first layer, a liquidor solid form of a spin-on-dielectric disposed on the first layer, and amonolayer of nanostructures disposed on the first layer in thespin-on-dielectric.

Essentially all of the features noted for the methods above apply tothese embodiments as well, as relevant; for example, with respect tocomposition of the liquid and/or solid form of the spin-on-dielectric,first layer, substrate, and nanostructures. It is worth noting that themonolayer of nanostructures is typically a disordered monolayer, andthat the device optionally comprises two or more discrete monolayerarrays embedded in the solid form of the spin-on-dielectric, each ofwhich typically occupies a predetermined position. It is also worthnoting that the device optionally comprises a flash transistor (floatinggate memory MOSFET) or memory device. Thus, in certain embodiments, thefirst layer comprises a dielectric material, such as an oxide (e.g., ametal oxide, silicon oxide, hafnium oxide, or alumina (Al₂O₃)), anitride, an insulating polymer, or another nonconductive material. Inthis class of embodiments, the first layer (which serves as a tunneldielectric layer) is preferably thin (e.g., has a thickness of betweenabout 1 nm and about 10 nm, e.g., between 3 and 4 nm), and is disposedon a substrate that comprises a semiconductor (e.g., a Si substrate).The substrate typically includes a source region, a drain region, and achannel region between the source and drain regions and underlying themonolayer array of nanostructures. A control dielectric layer isdisposed on the monolayer of nanostructures in the spin-on-dielectric,if needed, and a gate electrode is disposed on the control dielectriclayer. The control dielectric layer comprises a dielectric material,e.g., an oxide (e.g., a metal oxide, SiO₂, or Al₂O₃), an insulatingpolymer, or another nonconductive material. The electrodes can compriseessentially any suitable material(s). For example, the gate electrodecan comprise polysilicon, a metal silicide (e.g., nickel silicide ortungsten silicide), ruthenium, ruthenium oxide, or Cr/Au. Similarly, thesource and drain electrodes optionally comprise a metal silicide (e.g.,nickel silicide or tungsten silicide) or any of various barrier metalsor metal nitrides such as TiN, connecting to other metals such as copperor aluminum.

Solvent Annealing

One aspect of the invention provides solvent annealing methods that canbe used to improve monolayer quality. Quantum dots or othernanostructures are deposited on a surface, and solvent annealing is thenemployed: the nanostructures are exposed to solvent vapor, introducingsome short-range mobility to the nanostructures on the surface and thusallowing monolayer assembly quality to improve.

Accordingly, one general class of embodiments provides methods forforming a nanostructure array. In the methods, a first layer is providedand a population of nanostructures is deposited on the first layer. Thenanostructures deposited on the first layer are exposed to extrinsicsolvent vapor, whereby the nanostructures assemble into a monolayerarray.

To expose the nanostructures on the first layer to the solvent vapor, afirst solvent can be provided in liquid form (e.g., in a reservoirphysically distinct from the first layer). The first layer bearing thenanostructures is typically placed in a container, e.g., a closedcontainer, with the liquid first solvent. The first solvent (and thefirst layer) can be maintained at ambient temperature, but optionallythe first solvent is heated, e.g., to a temperature sufficient tovaporize at least a portion of the solvent. For example, the firstsolvent can be heated to a temperature greater than 30° C., greater than50° C., greater than 70° C., or greater than 90° C. Preferably, thistemperature is less than the boiling point of the solvent and is not sohigh as to result in fusion of the nanostructures with each other. Itwill be evident that heating can both vaporize the solvent and permitthe nanostructures on the surface to have greater mobility. The selectedtemperature is maintained for a sufficient time to permit monolayerformation. The first solvent is preferably one in which thenanostructures disperse well and that wets the first layer well.Suitable solvents include, but are not limited to, hexane, octane,xylene, chlorobenzene, methyl-isobutylketone (MIBK), and volatilesiloxanes.

The nanostructures can be deposited on the first layer by dispersingthem in a solution comprising at least one second solvent and disposingthe resulting solution on the first layer. The solution comprising thenanostructures can be applied to the first layer by essentially anytechnique known in the art, for example, spray coating, flow coating,capillary coating, dip coating, roll coating, ink-jet printing, spincoating, or other wet coating techniques. Optionally, the solution isdisposed on the first layer by a technique other than spin coating. Thesecond solvent in which the nanostructures are dispersed can be the sameas or different from the first solvent to whose vapor the nanostructuresare exposed after deposition on the first layer.

The nanostructures are optionally substantially dry when exposed to thesolvent vapor. Thus, in one class of embodiments, the methods includeevaporating the second solvent in which the nanostructures weredispersed to provide dry nanostructures deposited on the first layer,after disposing the solution on the first layer and prior to exposingthe nanostructures to the solvent vapor. The dry nanostructuresdeposited on the first layer are optionally exposed to air or to aselected atmosphere (e.g., an oxygen-containing atmosphere, N₂, CDA(compressed dry air), or the like), typically at ambient temperature,prior to exposing the nanostructures to the solvent vapor.

In another class of embodiments, the nanostructures are still wet withthe second solvent when they are exposed to the solvent vapor. Forexample, a thin film of second solvent can be permitted to remain on thefirst layer surrounding the nanostructures. In these embodiments,exposure to the solvent vapor of the first solvent decreases theevaporation rate of the second solvent from the surface, facilitatingassembly of the nanostructures.

The solvent vapor is extrinsically supplied, and thus arises from asource of first solvent extrinsic to the nanostructures and typicallythe first layer. For example, the solvent vapor does not arise from afilm of second solvent remaining on the first layer and surrounding thenanostructures.

In one class of embodiments, the number of nanostructures applied to thefirst layer is substantially equal to the number of nanostructuresdesired in the resulting monolayer array. Since excess nanostructuresneed not be applied, a washing step to remove excess nanostructuresafter monolayer formation is not required.

As for the other embodiments described herein, the first layer cancomprise essentially any desired material, e.g., a conductive material,a nonconductive material, a semiconductor, or the like, including, forexample, a silicon wafer or a flexible material such as a plastic. Thefirst layer optionally comprises a dielectric material such as an oxideor nitride, e.g., silicon oxide, hafnium oxide, alumina, or siliconnitride, and is optionally disposed on a substrate (in embodiments inwhich it is not serving as a substrate).

The first layer can be modified before deposition of the nanostructures,for example, with a compound that forms a self-assembled monolayer.Exemplary compounds include, but are not limited to, a mercaptosilane,APTES, OTS, and HMDS.

The resulting monolayer array of nanostructures can comprise an orderedarray or a disordered array. The array optionally has a density greaterthan about 1×10¹⁰ nanostructures/cm², greater than about 1×10¹¹nanostructures/cm², greater than about 1×10¹² nanostructures/cm² (e.g.,3−4×10¹² nanostructures/cm²), or greater than about 1×10¹³nanostructures/cm².

Essentially all of the features noted for the embodiments above apply tothese embodiments as well, as relevant; for example, with respect toincorporation of the array(s) into transistor(s), nanostructure shapeand composition, nanostructure ligands, size of the array(s), and thelike. For example, the nanostructures are optionally substantiallyspherical nanostructures or quantum dots. The nanostructures cancomprise essentially any desired material. In one class of embodiments,the nanostructures have a work function of about 4.5 eV or higher.

FIG. 9 presents micrographs of Pd quantum dots deposited on low stresssilicon nitride before (Panel A) and after (Panel B) solvent annealing.In this example, chlorobenzene is utilized as the annealing solvent. Thesolvent is heated to 110° C. for 12 hours, during which the dots onsubstrate are exposed to the chlorobenzene vapor. The solvent annealingprocess decreased the percentage of multi-layer regions and improved theassembly quality.

Monolayer formation is, as noted above, an important step in fabricatingany of a number of nanostructure-based devices, including quantumdot-based devices. Current techniques for forming quantum dot monolayerstypically use an excess of the dots. For example, when a wafer is spincoated with quantum dots, most of the dots are spun away into thechemical drain (typically, more than 95% of the dots). These excess dotscannot generally be recovered for reuse due to concerns aboutcontamination and quality control. Techniques that minimize dotconsumption are thus desirable, particularly for mass production ofnanostructure devices.

One aspect of the invention provides methods that facilitate monolayerformation while optionally minimizing consumption of nanostructures. Thesurface of interest (e.g., a wafer) is coated with quantum dots or othernanostructures. The surface can be spin-coated with dots, or optionallythe dots can be applied to the surface with a non-spinning technique.The dots can be applied to the surface in an amount calculated toproduce a desired density when the dots are in a monolayer on thesurface. To obtain a high-quality monolayer, solvent annealing isemployed after deposition of the dots: the dots are exposed to solventvapor, giving them short-range mobility and permitting them to move frommulti-layer regions to form a monolayer.

Patterning Monolayers Using Resist

Certain methods described above permit the size, shape, and/or positionof resultant monolayer nanostructure arrays to be predetermined Use ofresist, e.g., photoresist, can also facilitate such patterning ofmonolayer arrays.

One general class of embodiments provides methods for patterning ananostructure monolayer. In the methods, a monolayer of nanostructuresdisposed on a first layer is provided. Resist is disposed on themonolayer of nanostructures to provide a resist layer, and apredetermined pattern on the resist layer is exposed (e.g., to light, anelectron beam, x-rays, etc.), to provide exposed resist in at least afirst region of the resist layer and unexposed resist in at least asecond region of the resist layer. If a positive resist is utilized, theexposed resist and its underlying nanostructures are removed, and thenthe unexposed resist is removed without removing its underlyingnanostructures from the first layer. If instead a negative resist isutilized, the unexposed resist and its underlying nanostructures areremoved, and then the exposed resist is removed without removing itsunderlying nanostructures. Whether positive or negative resist is used,at least one nanostructure monolayer array defined by the first regionremains on the first layer. It will be evident that if a positive resistis used, the position of the array corresponds to that of the secondregion (i.e., the inverse of the first region), while if a negativeresist is used, the position of the array corresponds to that of thefirst region. The boundaries of the nanostructure monolayer array arethus defined by the boundaries of the first region.

The monolayer of nanostructures can be produced by any convenienttechnique. For example, the first layer can be spin coated with asolution of nanostructures, and any nanostructures which are not incontact with the first layer can then be removed, e.g., by washing.Monolayers can also be formed, e.g., by soaking or dip coating the firstlayer or by using a commercially available Langmuir-Blodgett device.

The first layer can, but need not, include a coating comprising ananostructure association group such as those described above, e.g., toincrease adherence of the nanostructures to the first layer. Similarly,the nanostructures optionally comprise a ligand such as those describedabove.

The resist can be disposed (e.g., by spin coating or other techniquesknown in the art) directly on the monolayer of nanostructures.Alternatively, one or more additional layers can be disposed between theresist and the monolayer. For example, in one class of embodiments, adielectric layer is disposed on the monolayer of nanostructures, and theresist is disposed on the dielectric layer.

The methods can be used to produce essentially any number of monolayerarrays. For example, when positive resist is used, the unexposed resistcan be provided in two or more, 10 or more, 50 or more, 100 or more,1000 or more, 1×10⁴ or more, 1×10⁶ or more, 1×10⁹ or more, 1×10¹⁰ ormore, 1×10¹¹ or more, or 1×10¹² or more discrete second regions of theresist layer, such that two or more, 10 or more, 50 or more, 100 ormore, 1000 or more, 1×10⁴ or more, 1×10⁶ or more, 1×10⁹ or more, 1×10¹⁰or more, 1×10¹¹ or more, or 1×10¹² or more discrete nanostructuremonolayer arrays remain on the first layer. Similarly, when negativeresist is used, exposed resist can be provided in two or more, 10 ormore, 50 or more, 100 or more, 1000 or more, 1×10⁴ or more, 1×10⁶ ormore, 1×10⁹ or more, 1×10¹⁰ or more, 1×10¹¹ or more, or 1×10¹² or morediscrete first regions of the resist layer, such that a like number ofdiscrete nanostructure monolayer arrays remains on the first layer.

Essentially all of the features noted for the methods above apply tothese embodiments as well, as relevant; for example, with respect tocomposition of the first layer, disposition of the first layer on asubstrate, composition of the substrate, incorporation of the array(s)into transistor(s), nanostructure shape and composition, size anddensity of the array(s), and the like. It is worth noting that themonolayer array (or each of multiple arrays) can comprise an orderedarray or a disordered array.

An exemplary embodiment is schematically illustrated in FIG. 4. In thisexample, first layer 420 (e.g., a 3-4 nm thick layer of SiO₂ or anotheroxide, nitride, or other nonconductive material) is disposed onsubstrate 421 (e.g., a Si or other semiconductor substrate). In step401, monolayer 422 of nanostructures (e.g., Pd quantum dots) is disposedon the first layer. In step 402, control dielectric layer 423 (e.g., anoxide such as SiO₂ or Al₂O₃, an insulating polymer, or anothernonconductive material) is disposed on the monolayer. (For example, anAl₂O₃ layer can be disposed by atomic layer deposition, or an SiO₂ layercan be disposed by chemical vapor deposition.) The control dielectriclayer is coated with a positive resist in step 403, masked and exposedin step 404, and developed in step 405 to remove the exposed resist. Insteps 406-408, source region 430 and drain region 431, which areseparated by channel region 437, are created in substrate 421 by ionimplantation (step 406), stripping off the unexposed resist (step 407),and activation (step 408). The control dielectric layer is again coatedwith positive resist (e.g., polymethyl methacrylate (PMMA)) to formresist layer 432, in step 409. In photolithography step 410, resist infirst regions 433 is exposed (e.g., by electron beam or deep UV), whileresist in second region 434 is protected by mask 435 and remainsunexposed. Exposed resist is removed in step 411 (e.g., developed withan organic solvent), then the portion of the control dielectric layerand first layer and the nanostructures underlying the exposed resist infirst region 433 are removed (e.g., by dipping in hydrofluoric acid) instep 412, leaving monolayer array of nanostructures 445. The boundariesof array 445 correspond to those of second region 434, and are thereforedefined by those of first region 433. In step 413, a metal layer isdisposed to form source electrode 440 and drain electrode 441. In step414, the unexposed resist is removed without disturbing the controldielectric layer or the nanostructures underlying it (e.g., bycontacting the unexposed resist with at least one solvent, e.g.,acetone). Gate electrode 442 (e.g., Cr/Au or another suitable material,including, but not limited to, polysilicon, a metal silicide (e.g.,nickel silicide or tungsten silicide), ruthenium, or ruthenium oxide) isthen disposed on the control dielectric layer in step 415, producingtransistor 450.

Another general class of embodiments also provides methods forpatterning a nanostructure monolayer. In the methods, a first layercomprising a resist layer disposed thereon is provided. The resist ispermitted to remain in at least a first region of the resist layer whilethe resist is removed from at least a second region of the resist layer.A population of nanostructures is disposed on the resist layer and thefirst layer; the nanostructures contact the resist in the first regionand the first layer in a second region. The resist and its overlyingnanostructures are removed from the first region, and any nanostructureswhich are not in contact with the first layer are removed from thesecond region, leaving at least one nanostructure monolayer arrayremaining on the first layer. It will be evident that the position,size, shape, etc., of the array corresponds to that of the secondregion, and that the number of arrays formed is equal to the number ofsecond regions.

The resist can disposed, exposed, and removed according to lithographytechniques well known in the art. Removal of the resist and itsoverlying nanostructures from the first region and of any nanostructureswhich are not in contact with the first layer (e.g., in the secondregion) is optionally accomplished simultaneously, for example, bywashing with at least a first solvent.

Essentially all of the features noted for the methods above apply tothese embodiments as well, as relevant; for example, with respect tocomposition of the first layer, coating of the first layer, dispositionof the first layer on a substrate, composition of the substrate,incorporation of the array(s) into transistor(s), nanostructure shapeand composition, nanostructure ligands, size and density of thearray(s), and the like. It is worth noting that the monolayer array (oreach of multiple arrays) can comprise an ordered array or a disorderedarray.

Yet another general class of embodiments also provides methods forpatterning a nanostructure monolayer. In the methods, resist and amonolayer of nanostructures embedded in the resist are disposed on afirst layer, to provide a resist layer. A predetermined pattern on theresist layer is exposed (e.g., to light, an electron beam, x-rays,etc.), to provide exposed resist in at least a first region of theresist layer and unexposed resist in at least a second region of theresist layer. If a positive resist is employed, the exposed resist andits embedded nanostructures are removed from the first layer withoutremoving the unexposed resist and its embedded nanostructures. If anegative resist is employed, the unexposed resist and its embeddednanostructures are removed from the first layer without removing theexposed resist and its embedded nanostructures. Whether positive ornegative resist is used, at least one nanostructure monolayer arraydefined by the first region remains on the first layer. It will beevident that if a positive resist is used, the position of the arraycorresponds to that of the second region (i.e., the inverse of the firstregion), while if a negative resist is used, the position of the arraycorresponds to that of the first region. The boundaries of thenanostructure monolayer array are thus defined by the boundaries of thefirst region.

The resist layer can be formed by essentially any convenient technique.For example, the first layer can be spin coated with a solutioncomprising the resist and the nanostructures.

The methods can be used to produce essentially any number of monolayerarrays. For example, when positive resist is used, the unexposed resistcan be provided in two or more, 10 or more, 50 or more, 100 or more,1000 or more, 1×10⁴ or more, 1×10⁶ or more, 1×10⁹ or more, 1×10¹⁰ ormore, 1×10¹¹ or more, or 1×10¹² or more discrete second regions of theresist layer, such that two or more, 10 or more, 50 or more, 100 ormore, 1000 or more, 1×10⁴ or more, 1×10⁶ or more, 1×10⁹ or more, 1×10¹⁰or more, 1×10¹¹ or more, or 1×10¹² or more discrete nanostructuremonolayer arrays remain on the first layer. Similarly, when negativeresist is used, exposed resist can be provided in two or more, 10 ormore, 50 or more, 100 or more, 1000 or more, 1×10⁴ or more, 1×10⁶ ormore, 1×10⁹ or more, 1×10¹⁰ or more, 1×10¹¹ or more, or 1×10¹² or morediscrete first regions of the resist layer, such that a like number ofdiscrete nanostructure monolayer arrays remains on the first layer.

In one aspect, the resist comprises a silicon compound, and the exposedresist optionally comprises silicon oxide (e.g., SiO₂). For example, theresist can be a silsesquioxane, such as mercapto-propyl-cyclohexylpolyhedral oligomeric silsesquioxane, hydrogen silsesquioxane, methylsilsesquioxane, octavinyl dimethyl silyl silsesquioxane, octasilanesilsesquioxane, octavinyl-T8 silsesquioxane, aminopropylcyclohexylpolyhedral oligomeric silsesquioxane, acrylo silsesquioxane, ormethacrylo silsesquioxane, or a combination thereof. In one class ofembodiments, the silsesquioxane or silicate is photopolymerizable. Thenanostructures can, but need not, have a silsesquioxane or other ligandsuch as those noted herein bound to their surface.

Essentially all of the features noted for the methods above apply tothese embodiments as well, as relevant; for example, with respect tocomposition of the first layer, treatment of the first layer,disposition of the first layer on a substrate, composition of thesubstrate, incorporation of the array(s) into transistor(s),nanostructure shape and composition, size and density of the array(s),and the like. It is worth noting that the monolayer array (or each ofmultiple arrays) can comprise an ordered array or, typically, adisordered array.

The resist layer optionally includes a compound that increases thedielectric constant of the layer. For example, the resist layer caninclude a spin-on-dielectric (e.g., a compound such as aluminumi-propoxide, tri-methyl aluminum, tri-ethyl aluminum, hafniumt-butoxide, hafnium ethoxide, tetrabenzyl hafnium,tris(cyclopentadienyl) lanthanum,tris(i-propylcyclopentadienyl)lanthanum,pentakis(dimethylamino)tantalum, tantalum methoxide, or tantalumethoxide) along with a negative resist (e.g., hydrogen silsesquioxane),such that when the resist is exposed and the spin-on-dielectric iscured, the resulting matrix around the nanostructures has a dielectricconstant higher than that of exposed resist without the compound. Thenanostructures are optionally adjacent to or in physical or electricalcontact with the first layer, or optionally are completely surrounded bythe resist. The resist layer can also be utilized as a diffusionbarrier, e.g., to prevent the material comprising the nanostructuresfrom diffusing into the first layer or any underlying substrate during asubsequent high temperature processing step. For example, when metalnanostructures on an SiO₂ first layer are annealed at elevatedtemperatures, the metal can diffuse through the SiO₂ layer. With a highk dielectric layer in the middle of metal nanostructures and thesubstrate, the diffusion can be blocked. As just one example, a hafniumoxide-containing resist can help stabilize Ru nanostructures during anannealing step.

An exemplary embodiment is schematically illustrated in FIG. 10. In thisexample, in step 1001, resist 1024 and nanostructures 1023 are disposedon first layer 1020 to provide resist layer 1022. In step 1002, resistin first regions 1033 is exposed (e.g., by deep UV), while resist insecond regions 1034 is protected by mask 1035 and remains unexposed.Unexposed resist with its embedded nanostructures is removed (e.g.,developed with an organic solvent) in step 1003, leaving monolayerarrays 1045 of nanostructures embedded in exposed resist.

FIG. 11 presents micrographs illustrating monolayer arrays patternedinto the Nanosys, Inc. logo and the word “nano” using methods of theinvention. A silicon nitride membrane was spin coated with a solution ofruthenium nanodots and aminopropylcyclohexyl POSS (see FIG. 3 Panel C,where R is a cyclohexyl group) in xylene to obtain a monolayer of Rudots embedded in the aminopropylcyclohexyl POSS. The monolayer was thensubjected to electron beam patterning with the first regions (formingthe logo and “nano”) exposed to electron beam with beam intensity 400μC/cm². The unexposed aminopropylcyclohexyl POSS (and dots therein) wasthen washed away with chloroform to obtain the patterned structure shownin FIG. 11.

As described herein, incorporation of nanostructure arrays into devicessuch as flash transistors is highly desirable. Typically, non-volatilememory devices employing nanostructures such as metal nanocrystals orquantum dots for charge storage require a high, uniform density ofnanostructures having a uniform size distribution. Colloidal metalnanocrystals can be synthesized with a uniform size distribution andcoated on a surface with uniform density; however, at the hightemperatures typically employed in transistor fabrication processes(e.g., high-temperature annealing steps following ion implantation toactivate source and drain regions in substrates), metal dots tend tofuse with each other. Such fusion decreases uniformity and density ofthe nanostructure array and increases the size distribution of thenanostructures (see, e.g., FIG. 12 Panel A).

Among other benefits, the methods herein provide a way to protectnanostructures from such fusion: nanostructures in exposed resist can beprotected from fusion during subsequent exposure to elevatedtemperatures. Embedding nanostructures in resist can thus not onlyfacilitate patterning of the nanostructures, but can also help maintaintheir integrity.

FIG. 12 presents micrographs illustrating protection of nanostructuresfrom fusion at high temperature by exposed silsesquioxane resist.Monolayers of ruthenium dots in aminopropylcyclohexyl POSS (see FIG. 3Panel C, where R is a cyclohexyl group) were exposed to 950° C. for 20seconds in a nitrogen/hydrogen atmosphere. The silsesquioxane resist waseither not cured before exposure to 950° C. (Panel A), or cured with UV(ultraviolet light) in a nitrogen atmosphere for 15 minutes (Panel B) or100 minutes (Panel C) before exposure to 950° C. Density of the dots isabout 2.03×10¹²/cm² in Panel A, 2.34×10¹²/cm² in Panel B, and2.75×10¹²/cm² in Panel C (densities for the three samples werecomparable prior to heating at 950° C.). In the sample without UV curingof the silsesquioxane (Panel A), significant fusing of the quantum dots,deterioration of the film morphology, and decreased dot density are seenafter 950° C. annealing. In contrast, with prior UV curing of the resist(Panels B and C), dot size, morphology, and density can be maintained.Without limitation to any particular mechanism, UV irradiationcross-links the silsesquioxane, immobilizing the dots in a cross-linkedsilicate matrix, preventing them from being mobile during the hightemperature step and thus preventing them from fusing with each other.

Thus, when a negative resist is employed in the methods, in one aspectthe methods include, after exposure of the resist in the first regionand removal of unexposed resist from the second region, exposing thefirst layer, the exposed resist, and its embedded nanostructures toelevated temperature. Typically, the elevated temperature is at leastabout 300° C. (at which temperature metal dots began to fuse if notprotected by exposed resist), e.g., at least about 400° C., at leastabout 500° C., at least about 600° C., more typically at least about700° C., at least about 800° C., or at least about 900° C. For example,the first layer, the exposed resist, and its embedded nanostructures canbe exposed to a temperature of 950° C. or more, for example, during ahigh-temperature annealing step. The duration of exposure to theelevated temperature can be brief, e.g., less than thirty minutes, lessthan ten minutes, less than one minute, less than 45 seconds, less than30 seconds, or even 20 seconds or less (particularly forhigh-temperature annealing steps).

The resist is optionally cured (partially or completely) in one stepbefore exposure to the elevated temperature. In a particularly usefulaspect, however, the resist is incompletely cured by initial low dose orbrief exposure to pattern the monolayer, unexposed resist and undesirednanostructures embedded therein are removed, and the incompletely curedresist is then further cured with a second exposure to protect thenanostructures during subsequent exposure to high temperature. Thus, inone class of embodiments, the resist in the first region is exposed toionizing radiation (e.g., x-rays, UV light, or electron beam) sufficientto incompletely cure the resist in the first region, the unexposedresist and its embedded nanostructures are removed from the first layer(without removing the incompletely cured resist and its embeddednanostructures), then the incompletely cured resist in the first regionis exposed to ionizing radiation sufficient to further cure the resistin the first region, before exposure to the elevated temperature.Suitable conditions for curing a variety of resists are known in the artand/or can be empirically determined. As one example, e.g., for asilsesquioxane cured by UV (e.g., UV centered at 250 nm), the resist inthe first region can be exposed to about 10 mJ/cm²-1 J/cm² ultravioletlight (e.g. 1 J/cm²) to incompletely cure the resist in the first regionand then to about 1 J/cm²-50 J/cm² ultraviolet light (e.g., 10 J/cm²) tofurther cure the resist in the first region.

By protecting the nanostructures from fusion, the techniques of theinvention can maintain nanostructure density, size distribution,monolayer morphology, etc., during high temperature processing steps, asindicated above. Accordingly, in one class of embodiments, the densityof nanostructures in the monolayer array after exposure to elevatedtemperature (e.g., 300° C. or more) is at least 75% of the density ofnanostructures in the monolayer array before such exposure, moretypically, at least 90% or at least 95%. Optionally, the density isessentially unchanged during the heating step. Optionally, following theelevated temperature step, the monolayer array of nanostructures has adensity greater than about 1×10¹⁰ nanostructures/cm², e.g., greater thanabout 1×10¹¹ nanostructures/cm², greater than about 1×10¹²nanostructures/cm², at least 2×10¹² nanostructures/cm², at least2.5×10¹² nanostructures/cm², at least 3×10¹² nanostructures/cm², atleast 4×10¹² nanostructures/cm², at least 5×10¹² nanostructures/cm², oreven at least about 1×10¹³ nanostructures/cm².

As described herein, monolayers with minimal variation in nanostructuredensity over the monolayer can be prepared (for example, by spin coatinga substrate with nanostructures dispersed in a liquidspin-on-dielectric/resist). Since the exposed resist protects thenanostructures from fusion, uniformity of the monolayer can bemaintained during high temperature steps. Accordingly, in one class ofembodiments, density of the nanostructures in the monolayer array issubstantially uniform following the exposure to the elevatedtemperature. Optionally, variation in density of the nanostructures inthe monolayer array is less than 10% across the monolayer, as indicatedabove, for example, as measured by comparing 25 nm squares within anarray (or between arrays formed from a single monolayer).

In a related class of embodiments, the average diameter of thenanostructures in the monolayer array after exposure to the elevatedtemperature is less than 110% of the average diameter of thenanostructures in the monolayer array before such exposure, for example,less than 105% or less than 103%. Optionally, the size distribution ofthe nanostructures in the array is essentially unchanged during theheating step.

In another related class of embodiments, following the exposure toelevated temperature, the size distribution of the nanostructures in themonolayer array exhibits an rms deviation of less than 20%. For example,the size distribution of the nanostructures in the monolayer array canexhibit an rms deviation of less than 15%, less than 10%, or even lessthan 5%. The narrow size distributions achievable by colloidal synthesisof nanostructures can thus be maintained through high temperatureprocessing step(s).

It will be evident that the tendency of nanostructures to fuse isgreater at higher initial nanostructure densities, and thus protectionfrom fusion is increasingly important with increasing nanostructuredensity. Thus, in embodiments in which preservation of nanostructuredensity, monolayer uniformity, nanostructure size, nanostructure sizedistribution, and/or the like is of interest, the density ofnanostructures in the monolayer array before exposure to the elevatedtemperature is optionally at least about 1×10¹⁰ nanostructures/cm²,e.g., at least about 1×10¹¹ nanostructures/cm², at least about 1×10¹²nanostructures/cm², at least 2×10¹² nanostructures/cm², at least2.5×10¹² nanostructures/cm², at least 3×10¹² nanostructures/cm², atleast 4×10¹² nanostructures/cm², at least 5×10¹² nanostructures/cm², oreven at least about 1×10¹³ nanostructures/cm².

As described above, the methods offer a convenient way to protect aswell as to pattern nanostructures. The methods also offer anotherrelated advantage; in certain embodiments (e.g., with silsesquioxaneresists), the unexposed resist and its embedded nanostructures isremoved from the first layer by contacting the unexposed resist with atleast one organic solvent. Washing the unexposed resist and embeddedundesired nanostructures off with solvent is very gentle compared toetching away unwanted nanostructures, as is required with PVD dots.Avoiding the etching step avoids potential damage to the first layer onwhich the nanostructures are deposited, for example, a sensitive tunneloxide layer.

As previously indicated, the methods optionally include incorporation ofthe array(s) into transistor(s). Thus, for example, the methodsoptionally include forming a source region and a drain region in thesubstrate in proximity to the monolayer array of nanostructures byimplanting dopant ions in the substrate, wherein implantation damage tothe substrate is repaired and the dopant is activated during theexposure to elevated temperature (high temperature annealing step). Agate electrode can be disposed on the exposed resist, after or,typically, before the high temperature annealing step. The exposedresist in which the nanostructure array is embedded optionally comprisesa dielectric material. The exposed resist can, in some embodiments,serve as a control dielectric. In other embodiments, a dielectric layeris disposed on the exposed resist (whether the exposed resist is itselfa dielectric material or not).

An exemplary embodiment is schematically illustrated in FIG. 13. In thisexample, first layer 1320 (e.g., a 3-4 nm thick layer of SiO₂ or anotheroxide, nitride, or other nonconductive material) is disposed onsubstrate 1321 (e.g., a Si or other semiconductor substrate). In step1301, resist layer 1329 including monolayer 1322 of nanostructures(e.g., metal quantum dots) embedded in resist 1328 (e.g., asilsesquioxane) is disposed on the first layer. For example, the firstlayer can be spin coated with nanostructures dispersed in the resist. Inphotolithography step 1302, resist in first region 1333 is exposed andincompletely cured (e.g., by electron beam or UV), while resist insecond regions 1334 is protected by mask 1335 and remains unexposed.Unexposed resist is removed in step 1303 (e.g., washed off with anorganic solvent). In step 1304, the resist is further cured, forexample, by exposure to electron beam or UV at higher dose. Optionaladditional steps can be included to burn off organic substituents (e.g.,in embodiments in which a silsesquioxane with organic substituents isemployed as the resist) and/or to make the resulting matrix less porous;for example, the substrate can be maintained at 300-400° C. (e.g., for 5to 30 minutes; e.g., in an oxygen-containing environment, a nitrogenatmosphere, a nitrogen/hydrogen atmosphere such as forming gas, or watervapor) and then optionally at 950° C. (e.g., for about 20 seconds; e.g.,in a nitrogen or nitrogen/hydrogen atmosphere). In step 1305, controldielectric layer 1323 (e.g., an oxide such as SiO₂ or Al₂O₃, aninsulating polymer, or another nonconductive material), source electrode1340, drain electrode 1341, and gate electrode 1342 are deposited andlithographically defined. Finally, in step 1306, source region 1330 anddrain region 1331, which are separated by channel region 1337, arecreated in substrate 1321 by ion implantation and activation, producingtransistor 1350. The cured resist protects the nanostructures during thehigh temperature annealing step that activates the source and drainregions. As noted above, preferred tunnel and control dielectric layersand gate electrodes are described in U.S. patent application Ser. No.11/743,085 and U.S. Provisional Patent Application Ser. No. 60/931,488,respectively.

In any of the embodiments herein, one or more additional monolayers (ormonolayer arrays) are optionally disposed on the monolayer (or array)described. Thus, the methods optionally include disposing a secondmonolayer of nanostructures on the resist layer or on the exposedresist. Third, fourth, etc., monolayers can also be disposed on thesecond, third, etc. The various layers are optionally disposed and thenpatterned at the same time, or the first monolayer can be patternedbefore the second is disposed on it and then patterned, e.g.,essentially as described above. A dielectric layer is optionallydisposed between adjacent nanostructure monolayers.

A related general class of embodiments provides methods for protectingnanostructures from fusion during high temperature processing. Themethods include a) disposing the nanostructures and a silsesquioxane ona first layer, b) curing the silsesquioxane, to provide curedsilsesquioxane in which the nanostructures are embedded, and c) heatingthe first layer, the cured silsesquioxane, and its embeddednanostructures. The cured silsesquioxane can form a matrix thatsurrounds or separates the nanostructures and protects them from fusionduring the heating step, as described for the embodiments above.

The nanostructures and the silsesquioxane can be disposed on the firstlayer using essentially any convenient technique. For example, the firstlayer can be spin coated with a solution comprising the silsesquioxaneand the nanostructures. The nanostructures can, but need not, form amonolayer on the first layer.

The silsesquioxane can be cured by heating it, typically, attemperatures less than about 500° C. For example, the silsesquioxane canbe cured by exposure to a temperature between about 300° C. and 400° C.,e.g., for five to 30 minutes. In such embodiments, steps b) and c) canbe contemporaneous, or step c) can follow step b). As another example,the silsesquioxane can be cured by exposure to ionizing radiation (e.g.,x-ray, UV, or electron beam), typically prior to step c). In one classof embodiments, the silsesquioxane is exposed to ionizing radiationsufficient to essentially completely cure the silsesquioxane. Thesilsesquioxane is optionally cured in one step. In a particularly usefulaspect, however, the silsesquioxane is incompletely cured as thenanostructures are patterned and is then subsequently further cured.

Thus, in one class of embodiments, in step b) curing the silsesquioxanecomprises b) i) exposing the silsesquioxane to ionizing radiation in apredetermined pattern, whereby the silsesquioxane in at least a firstregion is exposed and incompletely cured while the silsesquioxane in aleast a second region remains unexposed and uncured, b) ii) removing theunexposed silsesquioxane and nanostructures therein from the secondregion without removing the incompletely cured silsesquioxane and itsembedded nanostructures from the first region, and b) iii) after stepii), exposing the incompletely cured silsesquioxane in the first regionto ionizing radiation to further cure the silsesquioxane, to provide thecured silsesquioxane. In one exemplary class of embodiments, in step b)i) the silsesquioxane in the first region is exposed to about 10mJ/cm²-1 J/cm² ultraviolet light (e.g., 1 J/cm², 250 nm) to incompletelycure the silsesquioxane in the first region, and in step b) iii) theincompletely cured silsesquioxane in the first region is exposed toabout 1 J/cm²-50 J/cm² ultraviolet light (e.g., 10 J/cm², 250 nm) tofurther cure the silsesquioxane in the first region. Unexposedsilsesquioxane and nanostructures therein can be removed from the secondregion without removing the incompletely cured silsesquioxane and itsembedded nanostructures from the first region by, e.g., contacting theunexposed silsesquioxane with at least one organic solvent.

After step b) iii) and before step c), the cured silsesquioxane isoptionally exposed to a temperature between about 300° C. and 400° C.(e.g., for 5 to 30 minutes; e.g., in an oxygen-containing environment, anitrogen atmosphere, a nitrogen/hydrogen atmosphere such as forming gas,or water vapor), and is then (or instead) optionally exposed to atemperature of about 950° C. (e.g., for about 20 seconds; e.g., in anitrogen or nitrogen/hydrogen atmosphere). The optional additionalstep(s) can be included to burn off organic substituents (in embodimentsin which a silsesquioxane with organic substituents is employed) and/orto make the resulting matrix less porous. Optionally, the methods resultin the nanostructures embedded in a matrix consisting essentially ofSiO₂ formed from the silsesquioxane.

Optionally, in step c) the first layer, the cured silsesquioxane, andits embedded nanostructures are exposed to a temperature of at leastabout 300° C. (typically, following step b), e.g., at least about 400°C., at least about 500° C., at least about 600° C., more typically atleast about 700° C., at least about 800° C., or at least about 900° C.For example, the first layer, the cured silsesquioxane, and its embeddednanostructures can be exposed to a temperature of 950° C. or more, forexample, during a high-temperature annealing step. The duration of theexposure can be brief, e.g., less than thirty minutes, less than tenminutes, less than one minute, less than 45 seconds, less than 30seconds, or even 20 seconds or less (particularly for high-temperatureannealing steps).

As noted above, the nanostructures disposed on the first layeroptionally comprise a monolayer. In embodiments in which a monolayer ispatterned in step b), in step b) ii) at least one nanostructuremonolayer array defined by the first region remains on the first layer.The methods can be used to produce essentially any number of monolayerarrays. For example, the exposed silsesquioxane can be provided in twoor more, 10 or more, 50 or more, 100 or more, 1000 or more, 1×10⁴ ormore, 1×10⁶ or more, 1×10⁹ or more, or 1×10¹² or more discrete firstregions, such that two or more, 10 or more, 50 or more, 100 or more,1000 or more, 1×10⁴ or more, 1×10⁶ or more, 1×10⁹ or more, or 1×10¹² ormore discrete nanostructure monolayer arrays remain on the first layer.

As described above, by protecting the nanostructures from fusion, themethods can maintain nanostructure density, size, size distribution,monolayer morphology, etc., during high temperature processing steps,whether or not the nanostructures are arrayed in a monolayer. Forexample, in one class of embodiments in which the nanostructures weredisposed in a monolayer, the density of nanostructures in the monolayerarray after step c) is at least 75% of the density of nanostructures inthe monolayer array before step c), more typically, at least 90% or atleast 95%. Optionally, the density is essentially unchanged during theheating step. As described above, protection from fusion is increasinglyimportant with increasing nanostructure density. Thus, the density ofnanostructures in the monolayer array before step c) is optionally atleast about 1×10¹⁰ nanostructures/cm², e.g., at least about 1×10¹¹nanostructures/cm², at least about 1×10¹² nanostructures/cm², at least2×10¹² nanostructures/cm², at least 2.5×10¹² nanostructures/cm², atleast 3×10¹² nanostructures/cm², at least 4×10¹² nanostructures/cm², atleast 5×10¹² nanostructures/cm², or even at least about 1×10¹³nanostructures/cm². In one class of embodiments, following step c), themonolayer array of nanostructures has a density greater than about1×10¹⁰ nanostructures/cm², e.g., greater than about 1×10¹¹nanostructures/cm², greater than about 1×10¹² nanostructures/cm², atleast 2×10¹² nanostructures/cm², at least 2.5×10¹² nanostructures/cm²,at least 3×10¹² nanostructures/cm², at least 4×10¹² nanostructures/cm²,at least 5×10¹² nanostructures/cm², or even at least about 1×10¹³nanostructures/cm². Optionally, density of the nanostructures in themonolayer array is substantially uniform following step c).

In one class of embodiments, the average diameter of the nanostructuresembedded in the cured silsesquioxane after step c) is less than 110% ofthe average diameter of the nanostructures embedded in the curedsilsesquioxane before step c), for example, less than 105% or less than103%. Optionally, the size distribution of the nanostructures embeddedin the cured silsesquioxane is essentially unchanged during step c). Ina related class of embodiments, the size distribution of thenanostructures embedded in the cured silsesquioxane exhibits an rmsdeviation of less than 20%. For example, following step c), the sizedistribution of the nanostructures embedded in the cured silsesquioxanecan exhibit an rms deviation of less than 15%, less than 10%, or evenless than 5%.

In embodiments in which the nanostructures are disposed in a monolayer,the methods optionally include disposing one or more additionalmonolayers on the monolayer. For example, in one class of embodiments,the methods include, after step b) i) and prior to step b) iii),disposing a second monolayer of nanostructures in silsesquioxane on theincompletely cured silsesquioxane. The second monolayer can then bepatterned as described for the first. As an alternative, the variouslayers can be disposed and then patterned simultaneously. A dielectriclayer is optionally disposed between adjacent nanostructure monolayers.

Essentially all of the features noted for the methods above apply tothese embodiments as well, as relevant; for example, with respect tocomposition of the first layer, treatment of the first layer,disposition of the first layer on a substrate, composition of thesubstrate, nanostructure shape and composition, size of the array(s),and the like. It is worth noting that, in embodiments in which monolayerarrays are produced, the monolayer array (or each of multiple arrays)can comprise an ordered array or, typically, a disordered array.

In embodiments in which one or more monolayer arrays are produced, themethods optionally include incorporating the array(s) intotransistor(s). Thus, for example, the methods optionally include forminga source region and a drain region in the substrate in proximity to themonolayer array by, prior to step c), implanting dopant ions in thesubstrate, wherein implantation damage to the substrate is repaired andthe dopant is activated during step c). A gate electrode can be disposedon the cured silsesquioxane, after or, typically, before the step c). Adielectric layer can be disposed on the cured silsesquioxane (i.e., onthe nanostructure array) before the gate electrode is disposed.

A variety of suitable silsesquioxanes have been described herein, suchas mercapto-propyl-cyclohexyl polyhedral oligomeric silsesquioxane,hydrogen silsesquioxane, methyl silsesquioxane, octavinyl dimethyl silylsilsesquioxane, octasilane silsesquioxane, octavinyl-T8 silsesquioxane,aminopropylcyclohexyl polyhedral oligomeric silsesquioxane, acrylosilsesquioxane, or methacrylo silsesquioxane, or a combination thereof.See also FIG. 3 Panels A-E. Additional silsesquioxanes are commerciallyavailable or readily produced by one of skill in the art.

In embodiments in which the nanostructures are metal nanostructures, ifthe nanostructures are oxidized and converted to a metal oxide during aheating step (particularly heating in an oxidizing atmosphere), they areoptionally subsequently reduced by heating them in a reducing atmosphere(e.g., an atmosphere comprising hydrogen, e.g., a forming gas).

As noted, devices produced by or useful in practicing the methods of theinvention are also a feature of the invention. Thus, another generalclass of embodiments provides a device comprising a first layer, amonolayer array of nanostructures disposed on the first layer, andresist disposed on the first layer. In one class of embodiments, theresist comprises a resist layer disposed on the monolayer array ofnanostructures. See, e.g., device 460 in FIG. 4. In another class ofembodiments, the resist occupies a first region of the first layer andthe monolayer array of nanostructures occupies a second region of thefirst layer, adjacent to the first region. In yet another class ofembodiments, the monolayer array of nanostructures is embedded in theresist (see, e.g., arrays 1045 in FIG. 10).

Essentially all of the features noted for the methods above apply tothese embodiments as well, as relevant; for example, with respect tocomposition of the first layer, coating of the first layer, dispositionof the first layer on a substrate, composition of the substrate,incorporation of the array(s) into transistor(s), nanostructure shapeand composition, nanostructure ligands, size and density of thearray(s), inclusion of a second monolayer disposed on the first, and thelike. It is worth noting that the monolayer array (or each of multiplearrays) can comprise an ordered array or a disordered array.

Devices for Monolayer Formation

One aspect of the invention provides devices and methods of using thedevices for forming nanostructure arrays. Thus, one general class ofembodiments provides a device comprising a first layer, a second layer,a cavity between the first and second layers, one or more spacers, andat least one aperture. The one or more spacers are positioned betweenthe first and second layers and maintain a distance between the firstand second layers. The at least one aperture connects the cavity with anexterior atmosphere. The cavity is occupied by a population ofnanostructures.

As will be described in greater detail below, the device can be used toform a nanostructure array. In brief, a solution of nanostructures isintroduced into the cavity, and the solvent is evaporated from thecavity. As the solvent evaporates, the nanostructures assemble into anarray on the first layer. The speed of evaporation can be controlled andslow, such that the nanostructures assemble into an ordered array.

Thus, in one class of embodiments, the nanostructures are dispersed inat least one solvent, while in other embodiments, the nanostructures aresubstantially free of solvent. The nanostructures optionally comprise anarray disposed on the first layer. The array can comprise a disorderedarray, but in certain embodiments, the array comprises an ordered array.The array preferably comprises a monolayer, e.g., an ordered monolayersuch as a hexagonal-close-packed monolayer, but optionally comprisesmore than a monolayer.

The first and second layers are typically substantially planar andsubstantially parallel to each other. Suitable materials for the firstlayer include, but are not limited to, those described above; forexample, a dielectric material such as an oxide (e.g., silicon oxide,hafnium oxide, and alumina) or a nitride. The first layer optionallyincludes a coating comprising a composition that includes ananostructure association group. Exemplary coating compositions andnanostructure association groups have been described above.

The first layer can be disposed on a substrate. Exemplary substrateshave also been described above; for example, a semiconductor substratecan be used if the resulting array of nanostructures is to beincorporated into a transistor or similar device. It will be evidentthat multiple devices can be disposed on a single substrate and used tosimultaneously produce essentially any desired number and/or size ofnanostructure arrays at predetermined positions on the substrate (e.g.,two or more, 10 or more, 50 or more, 100 or more, 1000 or more, 1×10⁴ ormore, 1×10⁶ or more, 1×10⁹ or more, 1×10¹⁰ or more, 1×10¹¹ or more, or1×10¹² or more arrays).

The second layer and/or the spacer(s) can comprise essentially anysuitable material. For example, the second layer and/or the spacer(s)can comprise a metal or a dielectric material (e.g., aluminum, nickel,chromium, molybdenum, ITO, a nitride, or an oxide).

The distance between the first and second layers is greater than anaverage diameter of the nanostructures. The distance can be about twotimes the average diameter of the nanostructures or more, although toencourage formation of a monolayer of nanostructures, in certainembodiments, the distance between the first and second layers is lessthan about two times the average diameter of the nanostructures. Forexample, for quantum dots having an average diameter of about 3-5 nm,the distance would be less than about 6-10 nm.

The device can be of essentially any desired size and/or shape. In oneclass of embodiments, the first layer has four edges. The first andsecond layers are separated by two spacers, which run along two oppositeedges of the first layer. Two apertures, which run along the remainingtwo opposite edges of the first layer, connect the cavity with theexterior atmosphere, e.g., to permit the solvent to escape as itevaporates. It will be evident that a large number of otherconfigurations are possible. As just one additional example, the firstlayer can have four edges and four corners, with a spacer at each cornerand an aperture along each edge, or the device can be circular,irregularly shaped, or the like.

Formation of the nanostructure array can be facilitated by applicationof an electric field across the cavity (see, e.g., Zhang et al., “Insitu observation of colloidal monolayer nucleation driven by analternating electric field” Nature 429:739-743 (2004)). Thus, in oneclass of embodiments, the first layer comprises or is disposed on afirst conductive material, and the second layer comprises or is disposedon a second conductive material. Conductive materials include, but arenot limited to, a metal, a semiconductor, ITO, and the like. Note thatthe presence of an insulating layer on either or both faces of thecavity (e.g., a dielectric first layer) does not preclude theapplication of such a field.

The nanostructures can comprise, e.g., short nanorods, substantiallyspherical nanostructures or quantum dots, and can comprise essentiallyany desired material. Nanostructures are described in greater detailbelow in the section entitled “Nanostructures”.

An example embodiment is schematically illustrated in FIG. 5, PanelsA-C. In this example, device 501 includes first layer 502, second layer503, cavity 504 between the first and second layers, and two spacers505. The spacers are positioned between the first and second layers andmaintain distance 506 between them. Two apertures 510 connect cavity 504with external atmosphere 513. The cavity is occupied by a population ofnanostructures 511, which in Panels A and B are dispersed in solvent512, while in Panel C, they comprise array 515 disposed on the firstlayer.

As noted, methods using devices of the invention form another feature ofthe invention. Thus, one general class of embodiments provides methodsfor forming a nanostructure array. In the methods, a device comprising afirst layer, a second layer, and a cavity between the first and secondlayers is provided. A solution comprising nanostructures dispersed in atleast one solvent is introduced into the cavity. At least a portion ofthe solvent is evaporated from the cavity, whereby the nanostructuresassemble into an array disposed on the first layer.

An exemplary method is schematically illustrated in FIG. 5, whichdepicts a cavity comprising nanostructures dispersed in a solvent inPanel A. The nanostructures draw together as the solvent evaporates(Panel B) and assemble into an array on the first layer (Panel C). Thesecond layer is removed (Panel D); in this example, the spacers are alsoremoved, leaving the nanostructure array disposed on the first layer.

The array is optionally incorporated into a device, e.g., a memorydevice; for example, the nanostructure array can comprise the gate areaof a flash transistor. It will be evident that the methods can be usedto form essentially any number of nanostructure arrays simultaneously,at predetermined positions (e.g., two or more, 10 or more, 50 or more,100 or more, 1000 or more, 1×10⁴ or more, 1×10⁶ or more, 1×10⁹ or more,1×10¹⁰ or more, 1×10¹¹ or more, or 1×10¹² or more).

Essentially all of the features noted for the devices above apply to themethods as well, as relevant; for example, with respect to configurationof the device; composition of the first layer and/or spacers; type ofnanostructures; configuration of the resulting array; and/or the like.

The device can be fabricated, e.g., using conventional lithographic,MEMS, and/or integrated circuit techniques. In one aspect, providing thedevice includes disposing a third layer on the first layer, disposingthe second layer on the third layer, and removing at least a portion ofthe third layer, whereby the cavity between the first and second layersis formed. The third layer or portion thereof can be removed, e.g., byetching away the third layer with an etchant, e.g., an anisotropicetchant. For example, the third layer can comprise polysilicon (i.e.,polycrystalline silicon), amorphous silicon, molybdenum or titanium, andthe etchant can comprise XeF₂.

It will be evident that the thickness of the third layer which isremoved defines the height of the resulting cavity between the first andsecond layers. Thus, the third layer has a thickness that is greaterthan an average diameter of the nanostructures. The third layer can havea thickness of about two times the average diameter of thenanostructures or more, although to encourage formation of a monolayerof nanostructures, in certain embodiments, the third layer has athickness that is less than about two times the average diameter of thenanostructures.

The first and second layers are typically separated by one or morespacers, which maintain the distance between the first and second layerswhen the third layer is removed. As noted, the resulting device can beof essentially any size and/or shape, so a large number ofconfigurations for the first, second, and third layers and the spacersare possible. For example, in one class of embodiments, the first layerhas four edges. The first and second layers are separated by twospacers, which run along two opposite edges of the first layer. Theresulting device thus has two apertures running along the remaining twoopposite ages. Alternatively, the device can have more or fewer spacers,spacers at corners instead of edges, can be circular or irregular inshape, and the like.

An exemplary method for providing a device is schematically illustratedin FIG. 6 Panel A. In this example, a relatively thick layer 610comprising, e.g., the same material as the desired first layer (e.g.,SiO₂ or another dielectric material) disposed on substrate 611 (e.g., aSi or other semiconductor substrate) is provided. In step 601, layer 610is masked and stripes are etched into it. In step 602, a thin layer ofmaterial is disposed to form first layer 612. In step 603, third layer613 is disposed on first layer 612 (e.g., a polysilicon third layer canbe disposed by chemical vapor deposition). In step 604, second layer 614is disposed on third layer 613 (e.g., a thin metal second layer can beevaporated onto the third layer). The thick, remaining portions of layer610 comprise spacers 615. In step 605, the third layer is etched away toleave cavities 616 in device 620. In this example, two devices arefabricated simultaneously on the same substrate.

Another exemplary method for providing a device is schematicallyillustrated in FIG. 6 Panel B. In this example, thin first layer 660 isprovided on substrate 661. In step 651, third layer 662 is disposed onfirst layer 660. In step 652, third layer 662 is masked and stripes areetched in it. In step 653, metal is deposited to form second layer 665and spacers 666. The device is optionally masked and etched in stripesperpendicular to those previously formed, to provide free edges for anetchant to access the third layer on opposite sides. In step 654, thethird layer is etched away to leave cavities 670 in device 671. Again,in this example, two devices are fabricated simultaneously on the samesubstrate.

The first layer optionally comprises a coating comprising a compositionincluding a nanostructure association group. Thus, the methodsoptionally include coating the first layer with a composition comprisinga nanostructure association group, prior to disposing the third layer onthe first layer. Exemplary coating compositions and nanostructureassociation groups have been described above.

Nanostructures can be conveniently introduced into the cavity by, e.g.,capillary action. In one class of embodiments, the solution ofnanostructures is introduced into the cavity by immersing the device inan excess of the solution, permitting the solution to be drawn into thecavity by capillary action, and removing the device from the excess ofthe solution.

Part or substantially all the solvent is evaporated. A rate ofevaporation of the solvent can be controlled, e.g., to control arrayformation. For example, slow evaporation of the solvent graduallyincreases the concentration of nanostructures, which can be conducive toformation of an ordered array of nanostructures, e.g., an orderedmonolayer such as a hexagonal-close-packed monolayer.

The process of solvent evaporation can create lateral motion of thenanostructures, which can contribute to formation of an ordered array.Additional motion of the nanostructures can be encouraged, e.g., byapplying an AC voltage across the cavity after introducing the solutioninto the cavity (e.g., prior to or simultaneous with evaporation of thesolvent). See Zhang et al. (supra), which indicates that an AC voltagecan generate eddy currents in the solution that give rise to lateralmotion of the nanostructures, contributing to formation of an orderedarray (e.g., a hexagonal-close-packed monolayer).

When evaporation and array formation have proceeded as far as desired,the second layer is removed. Optionally, any extraneous nanostructures(e.g., any nanostructures greater than a monolayer) and/or any remainingsolvent can also be removed, e.g., by washing. The second layer can, forexample, be etched away, or the spacers can be etched away and thesecond layer lifted off, e.g., by washing with a solvent, withoutdisturbing the nanostructure array. Similarly, a layer of resist can bedisposed on the spacers under the second layer, or under the spacers onthe first layer, to facilitate lifting off the second layer by soakingin a suitable solvent.

Another general class of embodiments provides a device including a solidsupport comprising at least one vertical discontinuity on its surface.The discontinuity comprises a protrusion from the surface or anindentation in the surface. The protrusion or indentation is at apredetermined position on the solid support. The device also includes apopulation of nanostructures disposed on the protrusion or in theindentation.

As will be described in greater detail below, the device can be used toform a nanostructure array. In brief, a solution of nanostructures isdeposited on the solid support, and the solvent is evaporated. As thesolvent evaporates, the nanostructures assemble into an array on theprotrusion or in the indentation. The speed of evaporation can becontrolled and slow, such that the nanostructures assemble into anordered array.

Thus, in one class of embodiments, the nanostructures are dispersed inat least one solvent, while in other embodiments, the nanostructures aresubstantially free of solvent. The nanostructures optionally comprise anarray disposed on the protrusion or in the indentation. The array cancomprise a disordered array, but in certain embodiments, the arraycomprises an ordered array. The array preferably comprises a monolayer,e.g., an ordered monolayer such as a hexagonal-close-packed monolayer,but optionally comprises more than a monolayer.

In a preferred class of embodiments, the solid support comprises a firstlayer. The solid support optionally also includes a substrate on whichthe first layer is disposed. In one class of embodiments, the firstlayer includes a coating comprising a composition comprising ananostructure association group. Exemplary materials for the first layerand substrate, and exemplary coating compositions and nanostructureassociation groups, have been described above. Essentially all of thefeatures noted in the embodiments above apply these embodiments as well,as relevant; for example, with respect to type of nanostructures (e.g.,short nanorods, substantially spherical nanostructures, quantum dots, orthe like).

It will be evident that a single solid support can comprise multipledevices, which can be used to simultaneously produce essentially anydesired number and/or size of nanostructure arrays at predeterminedpositions on the solid support (e.g., on a substrate comprising thesupport, e.g., two or more, 10 or more, 50 or more, 100 or more, 1000 ormore, 1×10⁴ or more, 1×10⁶ or more, 1×10⁹ or more, 1×10¹⁰ or more,1×10¹¹ or more, or 1×10¹² or more arrays).

Exemplary embodiments are schematically illustrated in FIG. 7, PanelsLetter A-C. In one example, device 701 comprises solid support 702,which includes first layer 708 and substrate 709. Surface 703 of solidsupport 702 includes a plurality of vertical discontinuities 704, whichcomprise protrusions 705 from the surface (Panels A-B). Panel B alsoillustrates a population of nanostructures 710, dispersed in solvent 711or in array 713, disposed on protrusions 705. In a second example,device 751 (Panel C) comprises solid support 752, which includes firstlayer 758 and substrate 759. Surface 753 of solid support 752 includes aplurality of vertical discontinuities 754, which comprise indentations755 in the surface.

The devices can be fabricated, e.g., using conventional lithographic,MEMS, and/or integrated circuit techniques, e.g., by masking and etchingthe first layer.

As noted, methods using devices of the invention form another feature ofthe invention. Thus, one general class of embodiments provides methodsfor forming a nanostructure array. In the methods, a solid supportcomprising at least one vertical discontinuity on its surface isprovided. The discontinuity comprises a protrusion from the surface oran indentation in the surface, and the protrusion or indentation is at apredetermined position on the solid support. A solution comprisingnanostructures dispersed in at least one solvent is deposited on thesolid support. At least a portion of the solvent is evaporated, wherebythe nanostructures assemble into an array disposed on the protrusion orin the indentation.

An exemplary method is schematically illustrated in FIG. 7 Panel B. Instep 721, a solution of nanostructures 710 in solvent 711 is depositedon solid support 702, which includes protrusions 705 from surface 703.As the solvent evaporates, the concentration of nanostructuresincreases. The solvent eventually de-wets the surface in some areas,clinging to the protrusions and de-wetting in the space between theprotrusions. Convection currents within the now-isolated droplets ofsolvent can provide lateral mobility to the nanostructures, facilitatingtheir self-assembly. Eventually, as evaporation proceeds, solventsurface tension results in a droplet of solvent remaining on top of theprotrusion (step 722). Substantially all of the solvent can beevaporated away, or evaporation can be halted once assembly of thenanostructures has reached the desired stage. Removal of any remainingsolvent, and optionally of any nanostructures greater than a monolayerand/or any nanostructures left in between the protrusions, leaves array713 of nanostructures disposed on the protrusion (step 723).

The array is optionally incorporated into a device, e.g., a memorydevice; for example, the nanostructure array can comprise the gate areaof a flash transistor. It will be evident that the methods can be usedto form essentially any number of nanostructure arrays simultaneously,at predetermined positions, e.g., two or more, 10 or more, 50 or more,100 or more, 1000 or more, 1×10⁴ or more, 1×10⁶ or more, 1×10⁹ or more,1×10¹⁰ or more, 1×10¹¹ or more, or 1×10¹² or more arrays.

Essentially all of the features noted for the devices above apply to themethods as well, as relevant; for example, with respect to configurationof the device, type of nanostructures, configuration of the resultingarray, and/or the like.

In a preferred class of embodiments, the solid support comprises a firstlayer. The solid support optionally also includes a substrate on whichthe first layer is disposed. The first layer optionally comprises acoating comprising a composition including a nanostructure associationgroup. Thus, the methods optionally include coating the first layer witha composition comprising a nanostructure association group, prior todepositing the solution on the first layer. Exemplary materials for thefirst layer and substrate, and exemplary coating compositions andnanostructure association groups, have been described above.

The solution containing the nanostructures can be deposited on the solidsupport by any of a variety of techniques, including, for example,spin-coating the solution on the solid support, dip-coating the solutionon the solid support, soaking the solid support in an excess of thesolution, or spray coating the solid support with the solution.

Part or substantially all the solvent is evaporated. A rate ofevaporation of the solvent can be controlled, e.g., to control arrayformation. For example, slow evaporation of the solvent graduallyincreases the concentration of nanostructures, which can be conducive toformation of an ordered array of nanostructures, e.g., an orderedmonolayer such as a hexagonal-close-packed monolayer.

Devices Including Nanostructure Arrays

The methods and devices described above can be used to producenanostructure arrays at predetermined positions, and these arrays can beincorporated into devices such as memory devices, LEDs, and the like.Thus, in one aspect, the invention provides devices includingnanostructure arrays, including arrays of predetermined location and/orsize.

One general class of embodiments provides a device that includes asubstrate and two or more nanostructure arrays disposed on thesubstrate. Each nanostructure array is disposed at a predeterminedposition on the substrate. As noted, the device is optionally producedby a method of the invention; exemplary devices are schematicallyillustrated in FIG. 1 (device 101) and FIG. 2 (device 201).

The substrate can comprise essentially any desired material, depending,e.g., on the desired use of the nanostructure arrays. Suitablesubstrates include, but are not limited to: a semiconductor; a uniformsubstrate, e.g., a wafer of solid material, such as silicon or othersemiconductor material, glass, quartz, polymerics, etc.; a large rigidsheet of solid material, e.g., glass, quartz, plastics such aspolycarbonate, polystyrene, etc.; a flexible substrate, such as a rollof plastic such as polyolefin, polyamide, and others; or a transparentsubstrate. Combinations of these features can be employed. The substrateoptionally includes other compositional or structural elements that arepart of an ultimately desired device. Particular examples of suchelements include electrical circuit elements such as electricalcontacts, other wires or conductive paths, including nanowires or othernanoscale conducting elements, optical and/or optoelectrical elements(e.g., lasers, LEDs, etc.), and structural elements (e.g.,microcantilevers, pits, wells, posts, etc.).

The nanostructures can, but need not be, in physical contact with thesubstrate. Thus, in one class of embodiments, a first layer is disposedbetween the nanostructure arrays and the substrate. Exemplary materialsfor the first layer have been described above. The first layeroptionally includes a coating comprising a composition including ananostructure association group; exemplary compositions andnanostructure association groups have likewise been described above.

In one class of embodiments, the first layer comprises a dielectricmaterial and has a thickness of between about 1 nm and about 10 nm,e.g., between 3 and 4 nm. The first layer can serve as a tunneldielectric layer in embodiments in which the nanostructure arrays areincorporated into flash transistors or memory devices, for example.Thus, in some embodiments, for each monolayer array of nanostructures,the substrate comprises a source region, a drain region, and a channelregion between the source and drain regions and underlying the monolayerarray of nanostructures; a control dielectric layer is disposed on eachmonolayer array of nanostructures; and a gate electrode is disposed oneach control dielectric layer. Preferred tunnel and control dielectriclayers and gate electrodes are described in U.S. patent applicant Ser.No. 11/743,085 and U.S. Provisional Patent Applicant Ser. No.60/931,488, respectively.

The device can include essentially any number of nanostructure arrays,for example, 10 or more, 50 or more, 100 or more, 1000 or more, 1×10⁴ ormore, 1×10⁶ or more, 1×10⁹ or more, 1×10¹⁰ or more, 1×10¹¹ or more, or1×10¹² or more nanostructure arrays. Similarly, the arrays can be ofessentially any desired size and/or shape. For example, eachnanostructure array can have an area of about 10⁴ μm² or less, about 10³μm² or less, about 10² μm² or less, about 10 μm² or less, about 1 μm² orless, about 10⁵ nm² or less, about 10⁴ nm² or less, or even about 4225nm² or less, about 2025 nm² or less, about 1225 nm² or less, about 625nm² or less, or about 324 nm² or less. Each nanostructure arrayoptionally has dimensions of about 45×45 nm or less, about 35×35 nm orless, about 25×25 nm or less, or about 18×18 nm or less.

In one aspect, each nanostructure array comprises an ordered arrayand/or a monolayer, e.g., a hexagonal-close-packed monolayer. For manyapplications, however, ordered arrays are not required. For example, forarrays for use in memory devices, the nanostructures need not be orderedin the arrays as long as they achieve sufficient density in disorderedarrays. Thus, in another aspect, each nanostructure array comprises adisordered array, e.g., a disordered monolayer array. The nanostructurearrays (e.g., disordered monolayer arrays) are optionally embedded in asolid form of a spin-on-dielectric or a solid form of a spin-on-glass.

In one class of embodiments, the arrays have a high density ofnanostructures. For example, each nanostructure array optionally has adensity greater than about 1×10¹⁰ nanostructures/cm², greater than about1×10¹¹ nanostructures/cm², greater than about 1×10¹² nanostructures/cm²,at least 2×10¹² nanostructures/cm², at least 2.5×10¹²nanostructures/cm², at least 3×10¹² nanostructures/cm², at least 4×10¹²nanostructures/cm², at least 5×10¹² nanostructures/cm², or even greaterthan about 1×10¹³ nanostructures/cm².

It will be evident that essentially any of the features described hereinapply in any relevant combination; for example, a device having two ormore disordered monolayer arrays, each with a density of greater thanabout 1×10¹¹ nanostructures/cm², disposed at predetermined positions ona substrate is a feature of the invention.

In one class of embodiments, the nanostructures comprise substantiallyspherical nanostructures or quantum dots. The nanostructures cancomprise essentially any desired material, chosen, e.g., based on thedesired application. For example, the nanostructures can comprise aconductive material, a nonconductive material, a semiconductor, and/orthe like. In one aspect, the nanostructures comprising the arrays have awork function of about 4.5 eV or higher. Such nanostructures are useful,for example, in fabrication of memory devices, where if the workfunction of the nanostructures is not sufficiently high, electronsstored in the nanostructures tend to travel back across the tunneldielectric layer, resulting in memory loss. Thus, the nanostructures(e.g., the substantially spherical nanostructures or quantum dots)optionally comprise materials such as palladium (Pd), iridium (Ir),nickel (Ni), platinum (Pt), gold (Au), ruthenium (Ru), cobalt (Co),tungsten (W), tellurium (Te), iron platinum alloy (FePt), or the like.The nanostructures comprising the arrays are typically preformed, thatis, synthesized prior to their incorporation in the array. For example,in one aspect, the nanostructures are colloidal nanostructures. In oneclass of embodiments, each of the nanostructures comprising the arrayscomprises a coating comprising a ligand associated with a surface of thenanostructure, e.g., a silsesquioxane ligand such as those described inU.S. Provisional Patent Application Ser. No. 60/632,570 (supra) orillustrated in FIG. 3 Panels A-C. In a related class of embodiments, thenanostructures comprising the arrays are encompassed by SiO₂ or otherinsulating shells, produced, e.g., from a silsesquioxane coating (seeU.S. Provisional Patent Application Ser. No. 60/632,570). Such ligandsor shells optionally control spacing between adjacent nanostructures inthe arrays. Nanostructures are described in greater detail below in thesection entitled “Nanostructures”.

A related general class of embodiments also provides a device thatincludes a substrate and two or more nanostructure arrays disposed onthe substrate. The substrate comprises a semiconductor, and eachnanostructure array comprises a monolayer and is disposed at apredetermined position on the substrate. For each monolayer array, thesubstrate comprises an activated source region, an activated drainregion, and a channel region between the source and drain regions andunderlying the monolayer array of nanostructures. When dopant ions(e.g., B or As) are implanted into source and drain regions of asubstrate (e.g., Si), damage to the substrate lattice typically occursand the dopant typically assumes an interstitial position in thelattice. As described above, a high-temperature annealing step istypically used to repair such implantation damage to the substrate andto activate the source and drain regions. In “activated” source anddrain regions, the dopant has taken substitution position in thesubstrate lattice, making the source and drain regions highly conductive(since the dopant, e.g., contributes extra electrons in the conductionband or extra holes in the valence band).

Suitable substrates include, but are not limited to, a quartz substrateor a silicon wafer or a portion thereof. As for the embodiments above,the substrate optionally includes other compositional or structuralelements that are part of an ultimately desired device.

In one class of embodiments, a first layer is disposed between themonolayer arrays and the substrate. Exemplary materials for the firstlayer have been described above. The first layer optionally includes acoating; exemplary coatings have likewise been described above. In oneclass of embodiments, the first layer comprises a dielectric materialand has a thickness of between about 1 nm and about 10 nm, e.g., between3 and 4 nm. The first layer can serve as a tunnel dielectric layer inembodiments in which the nanostructure arrays are incorporated intoflash transistors or memory devices, for example. Thus, in someembodiments, a control dielectric layer is disposed on each monolayerarray of nanostructures, and a gate electrode is disposed on eachcontrol dielectric layer. As noted for the embodiments above, preferredtunnel and control dielectric layers and gate electrodes are describedin Chen U.S. patent application Ser. No. 11/743,085 and U.S. ProvisionalPatent Application Ser. No. 60/931,488, respectively.

Essentially all of the features noted for the embodiments above apply tothese embodiments as well, as relevant; for example, with respect tonanostructure shape and composition, inclusion of preformednanostructures, number of arrays, size and/or dimensions of the arrays,and the like. It is worth noting that the arrays can be ordered arraysor, more typically, disordered arrays. The nanostructure arrays areoptionally embedded in a solid form of a spin-on-dielectric or a solidform of a spin-on-glass, a cured (partially or essentially completelycured) resist, a cured silsesquioxane, silicon dioxide, or the like, asdescribed above.

The device is optionally produced by a method of the invention, andthus, as described above, can include nanostructures with a narrow sizedistribution. Thus, in one class of embodiments, the size distributionof the nanostructures in the monolayer arrays exhibits an rms deviationof less than 20%, for example, less than 15%, less than 10%, or evenless than 5%.

In one class of embodiments, the arrays have a high density ofnanostructures. For example, each nanostructure array optionally has adensity greater than about 1×10¹° nanostructures/cm², greater than about1×10¹¹ nanostructures/cm², greater than about 1×10¹² nanostructures/cm²,at least 2×10¹² nanostructures/cm², at least 2.5×10¹²nanostructures/cm², at least 3×10¹² nanostructures/cm², at least 4×10¹²nanostructures/cm², at least 5×10¹² nanostructures/cm², or even greaterthan about 1×10¹³ nanostructures/cm². Optionally, as described above,density of the nanostructures in each monolayer array (or betweenarrays) is substantially uniform.

In one class of embodiments, each of the two or more monolayer arrays ofnanostructures disposed on the substrate has an additional monolayerarray (or two or more additional arrays) of nanostructures disposedthereon. A dielectric layer is optionally disposed between adjacentmonolayers. A control dielectric layer and gate electrode can bedisposed on the second (or third, fourth, etc.) monolayer.

Use of nanostructures as storage elements in memory devices facilitatescreation of nodes smaller than those accessible by conventionalintegrated circuit fabrication techniques. Thus, another general classof embodiments provides a memory device that includes at least onetransistor (e.g., a MOSFET) comprising a gate area which is occupied bya monolayer array of nanostructures and which has an area of 8100 nm² orless. The gate area optionally has an area of about 4225 nm² or less,about 2025 nm² or less, about 1225 nm² or less, about 625 nm² or less,or even about 324 nm² or less. The gate area optionally has dimensionsof about 65×65 nm or less, about 45×45 nm or less, about 35×35 nm orless, about 25×25 nm or less, or about 18×18 nm or less.

The device can include essentially any number of such transistors. Forexample, the memory device can include two or more, 10 or more, 50 ormore, 100 or more, 1000 or more, 1×10⁴ or more, 1×10⁶ or more, 1×10⁹ ormore, 1×10¹⁰ or more, 1×10¹¹ or more, or 1×10¹² or more transistors.

Essentially all of the features noted for the embodiments above apply tothis embodiment as well, as relevant. For example, the nanostructurescomprising the monolayer array optionally comprise substantiallyspherical nanostructures or quantum dots, have a work function of about4.5 eV or higher, are preformed (e.g., colloidal), and/or areencompassed by SiO₂ or other insulating shells. Similarly, the monolayerarray can comprise an ordered array (e.g., a hexagonal-close-packedmonolayer) or a disordered array. The monolayer array (whether orderedor disordered) optionally has a density greater than about 1×10¹⁰nanostructures/cm², greater than about 1×10¹¹ nanostructures/cm²,greater than about 1×10¹² nanostructures/cm², at least 2×10¹²nanostructures/cm², at least 2.5×10¹² nanostructures/cm², at least3×10¹² nanostructures/cm², at least 4×10¹² nanostructures/cm², at least5×10¹² nanostructures/cm², or even greater than about 1×10¹³nanostructures/cm².

One exemplary embodiment is schematically illustrated in FIG. 4, inwhich memory device/transistor 450 includes monolayer array 445 ofnanostructures occupying gate area 449.

As noted, the methods of the invention facilitate high temperatureannealing of substrates while maintaining nanostructure size, density,etc. (for example, the narrow size distributions achievable by colloidalbut not PVD dots). Thus, one general class of embodiments provides amemory device that includes at least one transistor comprising a gatearea which is occupied by a monolayer array of nanostructures, anactivated source region, and an activated drain region, wherein the sizedistribution of the nanostructures in the monolayer array exhibits anrms deviation of less than 20%. For example, the size distribution ofthe nanostructures in the monolayer array can exhibit an rms deviationof less than 15%, less than 10%, or even less than 5%. Optionally,density of the nanostructures in the monolayer array is substantiallyuniform. The at least one transistor can comprise two or more, 10 ormore, 50 or more, 100 or more, 1000 or more, 1×10⁴ or more, 1×10⁶ ormore, 1×10⁹ or more, or 1×10¹² or more transistors.

Essentially all of the features noted for the embodiments above apply tothese embodiments as well, as relevant; for example, with respect tonanostructure shape and composition, inclusion of preformednanostructures, size and/or dimensions of the array, inclusion of asecond (third, fourth, etc.) monolayer array on the first, controldielectric, tunnel dielectric, gate electrode, and the like. It is worthnoting that the array can be ordered or, more typically, disordered. Themonolayer array (whether ordered or disordered) optionally has a densitygreater than about 1×10¹⁰ nanostructures/cm², greater than about 1×10¹¹nanostructures/cm², greater than about 1×10¹² nanostructures/cm², atleast 2×10¹² nanostructures/cm², at least 2.5×10¹² nanostructures/cm²,at least 3×10¹² nanostructures/cm², at least 4×10¹² nanostructures/cm²,at least 5×10¹² nanostructures/cm², or even greater than about 1×10¹³nanostructures/cm². The nanostructures in the array are optionallyembedded in a solid form of a spin-on-dielectric or a solid form of aspin-on-glass, a cured (partially or essentially completely cured)resist, a cured silsesquioxane, silicon dioxide, or the like, asdescribed above.

Additional details of nanostructure-based memory devices, transistors,and the like can be found, e.g., in U.S. Pat. No. 7,595,528.

Nanostructures

The individual nanostructures employed in the methods and devicesinclude, but are not limited to, a nanocrystal, a quantum dot, ananodot, a nanoparticle, a nanowire, a nanorod, a nanotube, ananotetrapod, a tripod, a bipod, a branched nanocrystal, or a branchedtetrapod. In one aspect, the methods and devices include spherical,nearly spherical, and/or isotropic nanocrystals such as nanodots and/orquantum dots, e.g., substantially spherical nanocrystals or quantum dotshaving an average diameter less than about 10 nm, and optionally lessthan about 8 nm, 6 nm, 5 nm, or 4 nm.

The nanostructures employed in the methods and devices of the presentinvention can be fabricated from essentially any convenient materials.For example, the nanocrystals can comprise inorganic materials, e.g., ametal, including, e.g., Pd, Ir, Ni, Pt, Au, Ru, Co, W, Te, Ag, Ti, Sn,Zn, Fe, FePt, or the like, or a semiconducting material selected from avariety of Group II-VI, Group III-V, or Group IV semiconductors, andincluding, e.g., a material comprising a first element selected fromGroup II of the periodic table and a second element selected from GroupVI (e.g., ZnS, ZnO, ZnSe, ZnTe, CdS, CdSe, CdTe, HgS, HgSe, HgTe, MgS,MgSe, MgTe, CaS, CaSe, CaTe, SrS, SrSe, SrTe, BaS, BaSe, BaTe, and likematerials); a material comprising a first element selected from GroupIII and a second element selected from Group V (e.g., GaN, GaP, GaAs,GaSb, InN, InP, InAs, InSb, and like materials); a material comprising aGroup IV element (Ge, Si, and like materials); a material such as PbS,PbSe, PbTe, AlS, AlP, and AlSb; or an alloy or a mixture thereof. Thenanostructures can include a p- or n-doped semiconductor. In otherembodiments, the nanostructures can include an insulating material(e.g., a metal oxide), a polymer, an organic material (e.g., carbon),and/or the like.

In one aspect, the nanostructures are preformed, i.e., fabricated priorto their use in the methods or incorporation into the devices. Forexample, the nanostructures can be colloidal nanostructures. Synthesisof colloidal metal nanostructures (e.g., Pd, Pt, and Ni nanostructures)is described in U.S. Provisional Patent Application Ser. No. 60/637,409,filed Dec. 16, 2004. Synthesis of colloidal III-V semiconductornanostructures is described in Scher et al. U.S. Pat. No. 7,557,028.Additional details of nanostructure synthesis have been described in theliterature (see, e.g., the following references).

Nanostructures can be fabricated and their size can be controlled by anyof a number of convenient methods that can be adapted to differentmaterials. For example, synthesis of nanocrystals of various compositionis described in, e.g., Peng et al., “Shape control of CdSenanocrystals,” Nature 404, 59-61 (2000); Puntes et al., “Colloidalnanocrystal shape and size control: The case of cobalt,” Science 291,2115-2117 (2001); Alivisatos et al. U.S. Pat. No. 6,306,736; Alivisatoset al. U.S. Pat. No. 6,225,198; Alivisatos et al. U.S. Pat. No.5,505,928; Alivisatos et al. U.S. Pat. No. 5,751,018; Gallagher et al.U.S. Pat. No. 6,048,616; and Weiss et al. U.S. Pat. No. 5,990,479.

Growth of nanowires having various aspect ratios, including nanowireswith controlled diameters, is described in, e.g., Gudiksen et al.,“Diameter-selective synthesis of semiconductor nanowires,” J. Am. Chem.Soc. 122, 8801-8802 (2000); Cui et al., “Diameter-controlled synthesisof single-crystal silicon nanowires,” Appl. Phys. Lett. 78, 2214-2216(2001); Gudiksen et al., “Synthetic control of the diameter and lengthof single crystal semiconductor nanowires,” J. Phys. Chem. B 105,4062-4064 (2001); Morales et al., “A laser ablation method for thesynthesis of crystalline semiconductor nanowires,” Science 279, 208-211(1998); Duan et al., “General synthesis of compound semiconductornanowires,” Adv. Mater. 12, 298-302 (2000); Cui et al., “Doping andelectrical transport in silicon nanowires,” J. Phys. Chem. B 104,5213-5216 (2000); Peng et al., “Shape control of CdSe nanocrystals,”Nature 404, 59-61 (2000); Puntes et al., “Colloidal nanocrystal shapeand size control: The case of cobalt,” Science 291, 2115-2117 (2001);Alivisatos et al. U.S. Pat. No. 6,306,736; Alivisatos et al. U.S. Pat.No. 6,225,198; Lieber et al. U.S. Pat. No. 6,036,774; Lieber et al. U.S.Pat. No. 5,897,945; Urbau et al., “Synthesis of single-crystallineperovskite nanowires composed of barium titanate and strontiumtitanate,” J. Am. Chem. Soc., 124, 1186 (2002); and Yun et al.,“Ferroelectric Properties of Individual Barium Titanate NanowiresInvestigated by Scanned Probe Microscopy,” Nanoletters 2, 447 (2002).

Growth of branched nanowires (e.g., nanotetrapods, tripods, bipods, andbranched tetrapods) is described in, e.g., Jun et al., “Controlledsynthesis of multi-armed CdS nanorod architectures using monosurfactantsystem,” J. Am. Chem. Soc. 123, 5150-5151 (2001); and Manna et al.,“Synthesis of Soluble and Processable Rod-, Arrow-, Teardrop-, andTetrapod-Shaped CdSe Nanocrystals,” J. Am. Chem. Soc. 122, 12700-12706(2000).

Synthesis of nanoparticles is described in, e.g., Clark, Jr. et al. U.S.Pat. No. 5,690,807; El-Shall et al. U.S. Pat. No. 6,136,156; Ying et al.U.S. Pat. No. 6,413,489; and Liu et al., “Sol-Gel Synthesis ofFree-Standing Ferroelectric Lead Zirconate Titanate Nanoparticles,” J.Am. Chem. Soc. 123, 4344 (2001).

The nanostructures optionally comprise a core-shell architecture.Synthesis of core-shell nanostructure heterostructures, namelynanocrystal and nanowire (e.g., nanorod) core-shell heterostructures,are described in, e.g., Peng et al., “Epitaxial growth of highlyluminescent CdSe/CdS core/shell nanocrystals with photostability andelectronic accessibility,” J. Am. Chem. Soc. 119, 7019-7029 (1997);Dabbousi et al., “(CdSe)ZnS core-shell quantum dots: Synthesis andcharacterization of a size series of highly luminescentnanocrysallites,” J. Phys. Chem. B 101, 9463-9475 (1997); Manna et al.,“Epitaxial growth and photochemical annealing of graded CdS/ZnS shellson colloidal CdSe nanorods,” J. Am. Chem. Soc. 124, 7136-7145 (2002);and Cao et al., “Growth and properties of semiconductor core/shellnanocrystals with InAs cores,” J. Am. Chem. Soc. 122, 9692-9702 (2000).Similar approaches can be applied to growth of other core-shellnanostructures.

Growth of nanowire heterostructures in which the different materials aredistributed at different locations along the long axis of the nanowireis described in, e.g., Gudiksen et al., “Growth of nanowire superlatticestructures for nanoscale photonics and electronics,” Nature 415, 617-620(2002); Bjork et al., “One-dimensional steeplechase for electronsrealized,” Nano Letters 2, 86-90 (2002); Wu et al., “Block-by-blockgrowth of single-crystalline Si/SiGe superlattice nanowires,” NanoLetters 2, 83-86 (2002); and Empedocles U.S. Patent Publication No.2004/0026684. Similar approaches can be applied to growth of otherhetero structures.

In certain embodiments, the collection or population of nanostructuresis substantially monodisperse in size and/or shape. See, e.g., Bawendiet al. U.S. Pat. No. 6,576,291.

Silsesquioxane and other ligand coatings for nanostructures, SiO₂shells, and oxidation of metal nanostructures are described in Whitefordet al. U.S. Pat. No. 7,267,875 and Whiteford et al. U.S. PatentPublication No. 2008/0118755.

While the foregoing invention has been described in some detail forpurposes of clarity and understanding, it will be clear to one skilledin the art from a reading of this disclosure that various changes inform and detail can be made without departing from the true scope of theinvention. For example, all the techniques and apparatus described abovecan be used in various combinations. All publications, patents, patentapplications, and/or other documents cited in this application areincorporated by reference in their entirety for all purposes to the sameextent as if each individual publication, patent, patent application,and/or other document were individually indicated to be incorporated byreference for all purposes.

The invention claimed is:
 1. A memory device comprising: at least one transistor comprising: a) a gate area occupied by a first monolayer array of nanostructures embedded in cured resist material, wherein a size distribution of the nanostructures in the first monolayer array exhibits an rms deviation of less than 20%; b) an activated source region; and c) an activated drain region.
 2. The memory device of claim 1, wherein the size distribution of the nanostructures in the first monolayer array exhibits an rms deviation of less than 15%.
 3. The memory device of claim 1, wherein the size distribution of the nanostructures in the first monolayer array exhibits an rms deviation of less than 10%.
 4. The memory device of claim 1, wherein density of the nanostructures in the first monolayer array is substantially uniform.
 5. The memory device of claim 1, wherein the at least one transistor comprises two or more, 10 or more, 50 or more, 100 or more, 1000 or more, 1×10⁴ or more, 1×10⁶ or more, 1×10⁹ or more, or 1×10¹² or more transistors.
 6. The memory device of claim 1, wherein the nanostructures comprising the first monolayer array comprise substantially spherical nanostructures or quantum dots.
 7. The memory device of claim 1, wherein the nanostructures comprising the first monolayer array have a work function of about 4.5 eV or higher.
 8. The memory device of claim 1, wherein the nanostructures comprise palladium, platinum, nickel, or ruthenium.
 9. The memory device of claim 1, wherein the nanostructures comprising the first monolayer array are preformed.
 10. The memory device of claim 1, wherein the first monolayer array has a density greater than about 1×10¹² nanostructures/cm².
 11. The memory device of claim 1, wherein the nanostructures in the first monolayer array are embedded in SiO₂.
 12. The memory device of claim 1, further comprising a second monolayer array of nanostructures disposed on the first monolayer array of nanostructures. 